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BOILERS FOR PEOPLE WHO KNOW AND CARE
 FEBRUARY 2011

HPIMPACT SPECIALREPORT TECHNOLOGY

Energy stocks offer CLEAN FUELS Updates on flare

positive returns New methods focus on systems and design
Advances in cellulosic “bottom-of-the-barrel” Consider new gas
biofuel production and clean fuels analysis techniques

www.HydrocarbonProcessing.com
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 FEBRUARY 2011 • VOL. 90 NO. 2
www.HydrocarbonProcessing.com

SPECIAL REPORT: CLEAN FUELS

33 HPI Viewpoint: Consumer protection is a key issue for E15

NPRA wants to be sure that adding greater amounts of ethanol to gasoline
is safe and will not cause engine damage 00 cutline for fig
C. T. Drevna

37 Slurry-phase hydrocracking—possible solution

to refining margins
Cover Neste Oil started up the world’s
largest and most advanced renewable
diesel plant in Singapore in November
Opportunity crudes require more hydrogen addition to upgrade 2010. The plant was completed
orphan product streams into higher-value ‘clean’ products on-schedule and on budget, and it is
located at the industrial area of Tuas,
M. Motaghi, B. Ulrich and A. Subramanian in the southwestern part of Singapore.
This facility has a production capacity
of 800,000 tons based on the Neste’s
45 Convert bottom-of-the-barrel into diesel and light olefins
Integrating residue hydrocracking operations with advanced fluid catalytic cracking
NExBTL renewable diesel process;
product is targeted for markets in
optimizes upgrading of heavy crude oils Europe and North America. Nest Oil is
constructing
00 a similar
cutline for fig sized renewable
M. Rama Rao, D. Soni, G. M. Sieli and D. Bhattacharyya NExBTL unit in Rotterdam with
start-up in the first half of 2011. Photo

51 What are the future fungible transportation fuels?

Alternatives hold promises to decrease dependence on crude oil,
courtesy of Neste Oil.

but they also uncover other challenges in distribution and engine use
M. Stockle

57 How to fabricate reactors for severe service

Many critical factors are involved in the design and welding of hydrocracking reactors
HPIMPACT
13 Energy stocks
D. Quintiliani, G. Fossataro and M. De Colellis
outperformed market
indices in 2010
63 Designing atmospheric crude distillation for bitumen service
Oil sands add complexity to separation units and require a new approach 15 Team overcomes
obstacles to cellulosic
M. Grande and M. Gutscher
biofuel production

71 Minimize carbon footprint from Claus tail-gas units

Reevaluate emissions efficiencies on sulfur-removal operations
M. P. Heisel and M. Rameshni

00 Cutline for fig.

COLUMNS
GAS PROCESSING DEVELOPMENTS 9 HPIN RELIABILITY
Alignment choices
79 Avoid these risks concerning combustion control
in fired heaters have consequences
Tuneable diode laser analyzers offer diagnostic benefits 11 HPINTEGRATION
R. Jenkins STRATEGIES
Data historians

PLANT SAFETY
HPIMPACT
provide effective
decision support in
XX near
Dewitt petrochemical-
real time
85 Circumvent design issues when adding
new hydrotreating units 94
conference out look
HPIN CONTROL
XX Six strategic business
Follow these guidelines for substantial capital cost savings with existing flare systems Inferential
technologiescontrol
to watch
model input selection
M. H. Marchetti XX Australia making
crucial GTL decisions
DEPARTMENTS
XX IEA assesses energy poli-
7 HPIN BRIEF • 19 HPINNOVATIONS • 25 HPIN CONSTRUCTION cies of U.S.
31 HPI CONSTRUCTION BOXSCORE UPDATE XX Creating more value in
90 HPI MARKETPLACE • 93 ADVERTISER INDEX capital projects

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 www.HydrocarbonProcessing.com

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 HPIN BRIEF
BILLY THINNES, NEWS EDITOR

[email protected]

Marathon Oil Corp. is moving forward with plans to spin ■ Ethanol

off Marathon’s downstream business, creating two independent energy companies.
Marathon Petroleum Corp. (MPC), to be headquartered in Findlay, Ohio, is expected to infrastructure
be the fifth largest US refiner with a downstream portfolio of strategically aligned assets lacking
concentrated mainly in the Midwest, Gulf Coast and Southeast regions of the US. The
spin-off is expected to be tax-free and to be effective June 30, 2011. Marathon Oil Corp. The US does not have the infra-
will be a global upstream company with a portfolio of assets delivering defined growth structure to meet the federal man-
leveraged to crude oil production and with exploration upside. It will continue to be date for renewable fuel use with
based in Houston, Texas. ethanol but could meet the standard
with significant increases in cellulosic
and next-generation biofuels, accord-
PetroChina International is forming a partnership with INEOS for
ing to a Purdue University study.
new trading and refining joint ventures related to refining operations in Grangemouth, The report’s authors used US
Scotland, and Lavéra, France. All companies will work toward the formation of the pro- Department of Energy (DOE) and
posed joint ventures by the end of June 2011. Underlying the international importance Environmental Protection Agency
of PetroChina’s and INEOS’ collaboration, the official signing ceremony for the agree- (EPA) data to determine that the US
ments was witnessed by Nick Clegg, the British deputy prime minister, and Li Ke Qiang, is at the “blending wall,” the satura-
the Chinese vice premier. The deal will create a strategic partnership between the two tion point for ethanol use. Without
companies, and INEOS believes it will improve the long-term sustainability of its refiner- new technology or a significant
increase in infrastructure, the study
ies, enhance security of supply for customers, and secure jobs in both the UK and France.
predicts that the country will not be
able to consume more ethanol than is
Axens North America has signed an agreement with Criterion being currently produced.
Catalysts and Technology and Shell that allows for the purchase of Criterion’s catalytic The US federal renewable fuel
reforming catalyst business. The specifics of the deal allow Axens to obtain Criterion’s standard requires an increase of
Willow Island, West Virginia, manufacturing plant for reforming catalyst and appropri- renewable fuel production to 36 bil-
ate intellectual property rights to pursue such business. lion gallons per year by 2022. About
13 billion gallons of renewable fuel
was required for 2010, the same
KBR and SK Innovation started up an advanced catalytic olefins
amount the report predicts is the
(ACO) demo plant in Ulsan, South Korea. Operations to date have met the companies’ threshold for US consumption.
expectations for olefins production, particularly propylene, with improved economics The study contends that there sim-
relative to steam cracking due to the technology’s higher total olefins yields and increased ply are not enough flex-fuel vehicles,
propylene/ethylene ratios approaching 1.0. The startup marks the first commercial dem- which use an 85% ethanol blend,
onstration of the ACO process. The demonstration unit achieved a design feed rate as or E85 stations to distribute more
scheduled in late October 2010. The ACO process provides an alternative to naphtha biofuels. According to EPA estimates,
steam crackers, and, according to KBR, not only does it offer higher olefins production, flex-fuel vehicles make up 7.3 million
of the 240 million vehicles on the
the process also produces a lower emissions footprint than a conventional cracker.
nation’s roads. Of those, about 3 mil-
lion of flex-fuel vehicle owners aren’t
Iraq’s South Oil Co. has awarded Emerson Process Management even aware they can use E85 fuel.
a contract to provide crude-oil metering systems and related technologies for the new There are only about 2,000 E85
Al-Basra oil terminal now under construction in the Persian Gulf. The new terminal, fuel pumps in the US, and it took
which includes both onshore and offshore facilities, will boost Iraq’s oil-export capacity more than 20 years to install them.
by 2.7 million bpd. The added capacity will give Iraq increased access to global markets In order for the US’ infrastructure
as it expands production from its southern oil fields. Emerson’s metering systems will to match the numbers in the fed-
eral mandate, the study’s authors say
measure the amount of oil as custody is transferred from producers to shippers through
2,000 pumps a year would need to
the Al-Basra terminal. The systems combine ultrasonic measurement technology with be installed through the year 2022.
diagnostic software that can detect potential problems before they affect accuracy. They also note that E85 needs to be
substantially cheaper than gasoline
Gushan Environmental Energy, a producer of biodiesel in China, to entice consumers to use it, because
is in the process of assessing the effect of a recently issued notice on consumption tax E85 gets lower mileage.
from the Chinese Ministry of Finance and the Chinese State Administration of Taxation. The report says that advances in
The notice regarding the exemption from consumption tax on pure biodiesel made from the production of thermo-chemical
biofuels, which are created by using
waste animal fats or vegetable oils was issued on December 24, 2010, and became effec-
heat to chemically alter biomass and
tive immediately. It clarifies that pure biodiesel made from waste animal fats or vegetable create fuels, would be necessary to
oils is exempted from consumption tax in China, and that such exemption will be imple- meet the renewable fuel standard. HP
mented retroactive to January 1, 2009. HP
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I7
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 HPIN RELIABILITY
HEINZ P. BLOCH, RELIABILITY/EQUIPMENT EDITOR

[email protected]

Alignment choices have consequences

Optimists tell us about steady industry trends toward reli- pump MTBR of a very marginal performer at 1.6 years, while best
ability-imparting procedures and work processes, while realists performers often get 9 years or more between pump failures. HP
continually make us aware of pressures to reduce expenditures.
As outside observers, we affirm that striving to reduce monetary LITERATURE CITED
1 Bloch, H. P. and A. Budris, Pump User’s Handbook: Life Extension, Third
outlay is quite commendable, but only as long as these aims don’t
Edition, 2010, Fairmont Press, Lilburn, GA 30047; (ISBN 0-88173-627-9).
run counter to the professed longer-term reliability improvement 2 Leibensperger, R. L.; “Look beyond catalog ratings,” Machine Design,
objectives. Conflicting issues are often alluded to in queries that April 3, 1975.
we receive from readers. For instance, we were asked if we knew
of literature that quantifies the merits of precision alignment for The author is Hydrocarbon Processing’s Reliability/Equipment Editor. A
pumps, and if it’s really appropriate to shun old-style methods. practicing consulting engineer with almost 50 years of applicable experience, he
advises process plants worldwide on failure analysis, reliability improvement and
maintenance. He has authored or co-authored 18 textbooks and close to 500
Modern vs. old school. With modern alignment methods papers or articles dealing with related subjects.
taking no more time than tinkering with old-style methods, com-
mon sense should point toward using precise methods. Inad-
equate alignment still causes major calamities (Fig. 1); whereas, 1.2
the results of sound alignment approaches typically show up as
improved mean time between repairs (MTBR) and a reduction 1.0
in maintenance outlay. The November 2006 HPIn Reliability
0.8
Life, of L10a %

column shed additional light on this topic.

A likely consensus among reasonable people holds that preci- 0.6
sion alignment typically lowers vibration to half of the value of
“conventional” alignment. Fig. 2 represents an estimate of bear- 0.4
ing operating life extension due to reduced vibration velocity for
typical process pumps. Fig. 3 gives an indication of how a major 0.2
bearing manufacturer rates the effects of misaligned bearings.
0.0
Most rolling element bearings fit somewhere between the two 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
curve boundaries and at tangents below 0.001; bearing life is Vibration, ips
thought to exceed a relative rating of 1.2 FIG. 2 Bearing housing vibration velocity vs. bearing life for
On average, there is then reason to believe that precision align- process pumps.1
ment alone would result in a pump MTBR multiplier of somewhere
between 1.4 and 1.7. The problem is that best-of-class performers
inevitably implement additional upgrades and they will seldom con- 1.50
fine their work to just better alignment. That is why Ref. 1 puts the
1.25

1.00
Relative bearing life

0.75

0.00

0.50

0.00
0.000 0.001 0.002 0.003 0.004 0.005 0.006
Tangent of misalignment angle
FIG. 1 Process pump failure that started with misalignment, high
vibration and bearing distress. Source: Murray & Garig Tool FIG. 3 How tangent of misalignment angle affects bearing life.
Works, Baytown, Texas.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I9
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 HPINTEGRATION STRATEGIES
ALLEN AVERY, CONTRIBUTING EDITOR

[email protected]

Data historians provide effective decision support

in near real time
Plant data historians are moving beyond their traditional role Historian suppliers have worked to offer improved data
as a tool for collecting and archiving data to better understand access and visibility tools with their solutions. Many offer web-
past plant performance, to becoming a powerful tool that can based, thin-client access to historians, and most offer access to
be used to improve real-time operations. With increased data historian data via mobile devices. Powerful trending and graph-
throughput and higher data resolutions, historians have also ics tools allow users to generate custom reports and charts to
become a foundation for plant asset management initiatives, visualize plant data. Suppliers have also emphasized ease of use
thanks to new visibility and trending tools that can also be used and configuration in their product development. Users can easily
to support energy management programs. Today’s historians also create custom interfaces and role-based dashboards to view and
support techniques, such as complex event processing, which can manipulate historian data.
analyze multiple streams of plant data in real time to identify and Due to their high data capture rates, today’s historians can
diagnose emerging problems before they disrupt the production act as a foundation for plant asset management programs.
process in the plant, or negatively affect smart grids or other The ability to store, access and analyze plant data in near real
distributed assets. time can help users identify any anomalies or troubling perfor-
mance trends that could indicate a problem with production
Plant historians get enhanced functionality. Recent equipment. Historical data can be used to develop models or
product advances increase historian data throughput, solution profiles that help users determine how a given asset should
scalability, compatibility and connectivity with plant systems behave under normal conditions, and to set alarms or formulate
and third-party solutions. They provide powerful visualization maintenance strategies to balance production needs with asset
and analytical tools. These allow users to access and leverage viability, remotely and in real time. We expect historians to
huge volumes of plant data in near real time. Historians can play a role in energy-management initiatives as well, by help-
collect and display real-time data and events, giving users a ing to develop energy-consumption models that can be used
more comprehensive view of what is happening in a plant or to identify under-performing and inefficient plant equipment,
distributed assets. Powerful processing capabilities, coupled with or to make real-time adjustments to production to minimize
advanced software algorithms, have changed how historians are energy costs.
used. Historians are transitioning from their traditional role, as
plant record-keepers and planners, to tools that can have a posi- Coming soon: Complex event processing. Though in
tive impact on plant operations in real time. its infancy, complex-event processing is another technology that
With recent advances in computing technology, includ- can harness the capabilities of plant historians. Historians can be
ing 64-bit processing architectures, historians can collect and used to complement and augment complex event processing, a
store large amounts of plant and process information. Many technology that can analyze multiple incoming streams of data
can archive up to several exabytes of data. Many can simul- in near real time. When viewed individually, these streams might
taneously store and retrieve plant data, giving users an up-to- mean little. But when viewed simultaneously and in context,
the-minute view of plant performance. Today’s historians can they could help identify process or plant equipment problems
handle hundreds of thousands of discrete events per second, so using advanced data filtering and algorithms.
real-time plant data is available almost immediately for analysis. ARC analysts are following recent trends in data historians
Modern computing power has enhanced historians to such a closely. These include the evolution of many plant historians
degree that, rather than just being used to look back on plant from large-capacity historical data repositories, to real-time
performance, they can be used to predict and positively impact decision-support and business intelligence platforms, and—ulti-
future performance. mately—to platforms that enable real-time operations centers
The use of de facto standards and environments, such as OPC functionality for a single plant or even a set of plants. HP read-
and Microsoft .NET, allows easier interfacing between systems ers should stay tuned to this column, or visit www.arcweb.com
and different historians. This helps users leverage existing his- for details on future reports on this important topic. HP
torian data, even if they choose a new solution from a different
vendor. OPC compatibility also enables easy access to, and use
of, data from HMI, DCS, CMMS and other plant-level appli-
Allen Avery is an analyst at ARC Advisory Group. His focus areas include field
cations. Since suppliers are also beginning to offer OPC-UA systems (flow, level, pressure, temperature and gas detection) and wireless networks.
compliant products, historian data is now also readily available to In addition, he covers plant asset management, energy management issues, and
applications running on non-Microsoft platforms. In addition to SCADA systems. He recently completed an extensive end-user study on energy
plant-level equipment, historians also interface well with EAM, management practices, and is the author of the report “SCADA Systems Oil & Gas
Industry Worldwide Outlook.”
ERP and advanced optimization applications.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 11
Süd-Chemie Defining the Future V Conference
May 23-25, 2011 – Beijing, China
Industry executives, technical experts and analysts will be discussing the latest innovations and breakthroughs in catalysis, process
engineering, battery materials and water treatment technologies applied in these fields at the “Defining the Future V Conference.”
Through open exchange and in-depth discussion, it is our goal to offer valuable insight into opportunities and challenges the industries
are facing, and to support the formulation of strategies that can be developed to address them. This conference will be comprised of
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• Refining Industries
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• Environmental Technologies
• Battery Materials
• Water Treatment Technologies
Please mark your calendar and join us in Beijing!

SÜD-CHEMIE
[email protected]
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 HPIMPACT
BILLY THINNES, NEWS EDITOR

[email protected]

Energy stocks interest rates fell to the lowest levels seen refining margins. BHP Billiton is the only
outperformed market in decades, which forced yield-conscious member of the 2009 crop to repeat in the
investors to take on more risk in order to top 10 this year.
indices in 2010 maintain their desired level of income.
Despite a poor start, 2010 finished as “The vast amount of liquidity being Natural gas. While oil stocks carried the
a “wonderful year” for energy investors, injected into the economic system, par- sector in 2010, continued weakness in the
with more than 65% of oil and gas stocks ticularly in the US, has resulted in a strong North American natural gas market did not
delivering positive returns last year, accord- correlation between equity prices and oil prevent the large producers from generating
ing to a report from IHS Herold. Driven by prices,” Mr. Gillon said. “By contrast, solid shareholder returns, with the median
economic growth, crude prices, which hit for many years prior to 2009, there was performance of the group nearly matching
bottom in late May 2010 at around $65 a reverse relationship, with higher crude that of the entire survey. However, a high
per barrel, rose steadily and consistently prices perceived to cause a reduction in dis- concentration of North American natural
through the second half of the year, and posable income, lower consumer spending, gas in the production mix detracted from
took oil company shares with them. and declining domestic product and stock returns, since US natural gas spot prices,
The median gain for the 503 stocks cov- prices. To our mind, this is the normal state which began the year at what now seems
ered in the report was 21%, which, while of affairs, but to predict we will be back to like the lofty price of $6/MMBtu, ended the
it did not match the record-setting 59% normal in short order would be unwise.” year at a nine-year low for the date, which
gain posted in the 2009 IHS report, did As a group, master limited partnerships was about 30% below where they began.
outperform the market indices of nearly (mostly pipeline and storage companies) “Natural gas inventories were well
all Organization for Economic Coopera- enjoyed a hearty gain of nearly 35%, while above average, and US domestic produc-
tion and Development (OECD) countries. the peer group of integrated oil stocks with tion showed no signs of topping out,” Mr.
Total capitalization jumped by more than
$300 billion, further reducing the severe
losses the sector incurred in 2008 the report ■ “The vast amount of liquidity being injected into the
said, but did not extinguish them. economic system, particularly in the US, has resulted in a
“Sometime in the first quarter of 2009, strong correlation between equity prices and oil prices,”
equity markets began to move upward in
response to the economic growth that was Mr. Gillon said. “By contrast, for many years prior to 2009,
becoming apparent in OECD countries,” there was a reverse relationship, with higher crude prices
said Robert Gillon, senior vice president perceived to cause a reduction in disposable income
and co-director of energy equity research
at IHS. “It seemed as though every statistic and lower consumer spending.”
that confirmed expansion was under way
was reflected in a rise in the price of crude, US downstream returned 22%, which was Gillon said. “Fortunately for everyone but
which boded well for oil stocks. That pat- marginally above the survey average. Cana- the Europeans, it has been ferociously cold
tern continued throughout the year, with dian integrated oil stocks and integrated oil in Europe, so gas is being shipped to the
oil prices and oil shares at a recovery high stocks without US downstream operations higher-priced markets. The world is well
at the closing bell of 2010. In particular, gained less than half that amount, at 10% supplied with gas, and the modest upward
North American oil stocks delivered the and 9%, respectively. Returns from the lat- slope to the current futures curve is testi-
most returns to their investors.” ter group, the report said, were dragged mony to the glut in supply.”
down by the generally poor performance
Group returns. After finishing second- of European markets. On the other hand, Alternative energy. Stocks in the alter-
to-last as a peer group in 2009, US royalty shares in the refining and marketing cat- native energy group held the basement
trusts earned redemption by taking top egory offered a healthy median gain of 38% position as worst in class, posting losses of
honors in 2010 as the best-performing and did well globally as demand for distil- more than 24% after gaining 26% in 2009.
peer group reviewed, posting a gain of more lates rose with increasing economic activity. “We’re not sure what to say about alter-
than 44%. MV Oil Trust led the group by Among the largest integrated and diver- native energy, except perhaps a requiem. In
posting a return of 111%. sified oils group, top-ranked Ecopetrol’s the five years we have shown this segment in
Companies in the E&P limited income 84% gain reflected rapidly growing oil pro- the survey, it has been the worst performing
partnerships group followed closely with duction, and it also got an updraft from group twice, second worst twice, and soared
gains of nearly 43%. According to the IHS the soaring Bogotá market. Sunoco Inc. to fourth from the bottom on one happy
report, these survey-leading returns were and Valero Energy, last year’s bottom two occasion,” Mr. Gillon said. “They suffer
in response to monetary stimuli by numer- performers in this grouping, moved into when natural gas prices go down, when gov-
ous central banks, where open-market the top 10 due to a dramatic turnaround in ernment subsidies are cut, when the wind
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 13
 Stepping up performance
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KPE
Select 77 at www.HydrocarbonProcessing.com/RS
 HPIMPACT
doesn’t blow, when it blows too much, and “Xylose is a wood sugar, a five-carbon glucose transporter on the surface of the
when the sun doesn’t shine. There may be sugar that is very abundant in lignocellu- yeast prefers to bind to glucose.
other problems, as well, which we will prob- losic biomass but not in our food,” said “It’s like giving meat and broccoli to my
ably find out about in 2011.” Yong-Su Jin, a professor of food science and kids,” he said. “They usually eat the meat
human nutrition at Illinois and a principal first and the broccoli later.”
Team overcomes investigator on the study. “Most yeast can- The yeast’s extremely slow metabolism
not ferment xylose.” of xylose also adds significantly to the cost
obstacles to cellulosic A big part of the problem with yeasts of biofuels production.
biofuel production altered to take up xylose is that they will Dr. Jin and his colleagues wanted to
A newly engineered yeast strain can suck up all the glucose in a mixture before induce the yeast to quickly and efficiently
simultaneously consume two types of sugar they will touch the xylose, Dr. Jin said. A consume both types of sugar at once, a pro-
from plants to produce ethanol, researchers
report. The sugars are glucose, a six-carbon
sugar that is relatively easy to ferment; and
xylose, a five-carbon sugar that has been
much more difficult to utilize in ethanol
production. The new strain, made by com-
bining, optimizing and adding to earlier
advances, reduces or eliminates several
major inefficiencies associated with cur-
rent biofuel production methods.
The findings, from a collaborative led
by researchers at the University of Illinois,
the Lawrence Berkeley National Labora-
tory, the University of California and BP,
are described in the Proceedings of the
National Academy of Sciences. The Energy
Biosciences Institute, a BP-funded initia-
tive, supported the research.

Yeast strains. Yeasts feed on sugar and

produce various waste products, some of
which are useful to humans. One type of
yeast, Saccharomyces cerevisiae, has been
used for centuries in baking and brewing
because it efficiently ferments sugars and,
in the process, produces ethanol and carbon
dioxide. The biofuel industry uses this yeast
MODERNIZING
to convert plant sugars to bioethanol. And Continuous Density
while S. cerevisiae is very good at utilizing
glucose, a building block of cellulose and
the primary sugar in plants, it cannot use
Catalyst Bed Reactor Measurement
xylose, a secondary—but significant—com-
ponent of the lignocellulose that makes up Maintaining an optimum level in the catalyst bed
plant stems and leaves. Most yeast strains reactor is critical for efficiency. The non-contact
that are engineered to metabolize xylose do MiniTrac 31 density detector provides accurate and
so very slowly. reliable measurement of layers within the reactor
while remaining unaffected by product variations,
ensuring efficient use of the expensive catalyst
without waste.
t
Mounts without interruption to the process
t
Measures through vessel walls and obstructions
t
Multiple density gauges measure across the
reactor span for optimized control
FIG. 1 Illinois University food science
and human nutrition professor
Yong-Su Jin, center, and his www.ohmartvega.com
colleagues engineered a yeast [email protected]
800.FOR.LEVEL
that outperforms the industry
standard.
KPE
Select 152 at www.HydrocarbonProcessing.com/RS
15
HPIMPACT
cess called co-fermentation. The research use in the biofuel industry. In fact, the new sumed in the same amount of time and
effort involved researchers from Illinois, the yeast strain simultaneously converts cel- produces more than double the amount
Lawrence Berkeley National Laboratory, lobiose (a precursor of glucose) and xylose of ethanol. It’s a huge synergistic effect of
the University of California at Berkeley, to ethanol just as quickly as it can ferment co-fermentation.”
Seoul National University and BP. either sugar alone. The new yeast strain is at least 20%
“If you do the fermentation by using more efficient at converting xylose to etha-
Adjustments. In a painstaking process only cellobiose or xylose, it takes 48 nol than other strains, making it “the best
of adjustments to the original yeast, Dr. Jin hours,” said post-doctoral researcher and xylose-fermenting strain” reported in any
and his colleagues converted it to one that lead author Suk-Jin Ha. “But if you do the study, Dr. Jin said.
will consume both types of sugar faster and co-fermentation with the cellobiose and
more efficiently than any strain currently in xylose, double the amount of sugar is con- Critical changes. The team achieved
these outcomes by making several critical
changes to the organism. First, they gave
the yeast a cellobiose transporter. Cellobi-
ose, a part of plant cell walls, consists of two
glucose sugars linked together. Cellobiose is
traditionally converted to glucose outside
the yeast cell before entering the cell through
glucose transporters for conversion to etha-
nol. Having a cellobiose transporter means
that the engineered yeast can bring cellobiose
#1 in Bearing Isolators directly into the cell. Only after the cellobi-
www.inpro-seal.com ose is inside the cell is it converted to glucose.
This approach eliminates the costly step
of adding a cellobiose-degrading enzyme to
the lignocellulose mixture before the yeast
consumes it.
It has the added advantage of circum-
venting the yeast’s own preference for glu-
cose. Because the glucose can now “sneak”
into the yeast in the form of cellobiose, the
glucose transporters can focus on drawing
xylose into the cell instead.

YOUR SAME-DAY SHIPMENT SPECIALISTS Bottleneck solutions. The team then

tackled the problems associated with xylose
When your equipment is down, you need a partner
that ships a solution to you same-day…not some day. metabolism. The researchers inserted three
At Inpro/Seal, we recognize the high cost of downtime genes into S. cerevisiae from a xylose-con-
facing our customers; that’s why we’ve designed our
operations to support quick–turnaround of our
suming yeast, Picchia stipitis. The team
custom–engineered bearing protection products. identified the bottleneck in this metabolic
With manufacturing locations in North America and
pathway. By adjusting the relative produc-
the United Kingdom, we’re able to offer industry– tion of these enzymes, the researchers elimi-
leading products with unparalleled response time nated the bottleneck and boosted the speed
and service to customers around the globe.
The right technology…right when you need it. of xylose metabolism in the new strain.
They also engineered an artificial “iso-
enzyme” that balanced the proportion of
two important co-factors so that the accu-
mulation of xylitol, a byproduct in the
xylose assimilitary pathway, could be mini-
mized. Finally, the team used “evolutionary
engineering” to optimize the new strain’s
ability to utilize xylose. The cost benefits
of this advance in co-fermentation are very
significant, Dr. Jin said.
“We don’t have to do two separate fer-
mentations,” he said. “We can do it all in
one pot. And the yield is even higher than
the industry standard. We are pretty sure
that this research can be commercialized
very soon.” HP
KPE
Select 153 at www.HydrocarbonProcessing.com/RS
16
 Advertisement

Sulzer Chemtech

Tower Technical Bulletin

Proper Design of Mass Transfer Internals in the FCC Flue Gas Scrubber Can Help
Reduce PM Emissions

Background fouling resistance and is designed to be self-draining to avoid any

The EPA’s New Source Performance Standards (40 C.F.R. solids trap-out problem. The Mellagrid smooth angles and transi-
§60.100-1-0, subpart Ja) regulates refinery particulate emissions, tions minimize shearing of liquid droplets, aiding in droplet settling.
including the discharge of catalyst fines from the FCCU flue gas
scrubber stack. The Sulzer F-GridTM or Nutter GridTM can be utilized as drop-in
replacements for an existing flue gas scrubber de-entrainment bed
Because refiners have traditionally correlated particulate matter during a turnaround, or Sulzer can customize the grid design for
(PM) emissions with FCCU cokeburn, high flue gas stack PM can optimum capacity, pressure drop, efficiency, and fouling resistance
result in reducing severity or throughput in the FCCU at a potentially with a combination bed.
huge economic cost. The proper selection of mass transfer internals
in the scrubber can contribute to its performance in controlling PM
emissions, and can improve the refinery’s bottom line.

A unit turnaround is a prime opportunity for the refiner to address

such issues as de-entrainment section fouling, chimney tray plug-
ging, and overall poor performance contributing to stack PM.

Removing Solids with a Flue Gas Scrubber

Flue gas scrubbing is one method to control particulate and SO2 in
FCCU flue gas vents. In scrubbers with external venturis, the flue Sulzer F-GridTM and Sulzer MellagridTM Grid Packing
gas is mixed with water and caustic to neutralize SOX. The com-
bined stream enters a disengaging drum through large venturis, Design of the Grid Wash Sprays
where centrifugal force is used to separate the liquid from the flue Scrubber packing is subject to plugging from the residual salts and
gas. The flue gas then travels upward toward the stack. A bed of catalyst fines that are removed from the flue gas. A set of wash sprays
structured grid packing is used to eliminate entrained droplets that is positioned above the bed for a periodic solids removal water wash.
contain particles of catalyst or salt. The condensate is collected
in a chimney tray and drained to the bottom of the disengaging High stack velocities can entrain the spraying wash water overhead,
drum. The scrubbed and de-entrained vapor is allowed to exit the not allowing adequate washing of the grid. Sulzer takes this into
scrubber stack. consideration in our design of the spray header, with the selection
of nozzle type and nozzle pressure drop keeping the droplet sizes
Design of the Chimney Tray large and preventing re-entrainment. The sprays would be designed
A Sulzer chimney tray design for flue gas scrubbing service fea- to fully cover the cross sectional grid area with sufficient overlap to
tures a sloping floor to prevent solids accumulation and multiple account for some droplet carry-up.
small chimneys. The open area is sized to minimize pressure drop,
while the riser arrangement allows for the best distribution into the
The Sulzer Refinery Applications Group
packed bed.
Sulzer Chemtech has over 50 years of operating and design experi-
ence in refinery applications. We understand your process and your
Selection of Packing
economic drivers. Sulzer has the know-how and the technology to
Grid-type structured packing is used in direct-contact heat trans-
provide a scrubber internals design with reliable, high performance.
fer, scrubbing, and de-entraining services such as the FCC flue gas
scrubber. Due to its high open area, grid has a very low pressure
drop and high capacity. Grids have low wetting rates compared with Sulzer Chemtech, USA, Inc.
structured packing, and can therefore achieve low turndowns. 8505 E. North Belt Drive | Humble, TX 77396
Phone: (281) 604-4100 | Fax: (281) 540-2777
An excellent option for de-entrainment in the flue gas stack is Sulzer [email protected]
MellagridTM, which has a smooth surface to provide the maximum www.sulzerchemtech.com

Legal Notice: The information contained in this publication is believed to be accurate and reliable, but is not to be construed as implying any warranty or guarantee of performance. Sulzer Chemtech
waives any liability and indemnity for effects resulting from its application.

KPE
Select 68 at www.HydrocarbonProcessing.com/RS
CRYO-PLUS™
Get More Valuable Liquid from your Gas Streams
Linde Process Plants, Inc. provides engineering, design, Why choose Linde’s CRYO-PLUS™
fabrication and construction of cryogenic plants for the – Proprietary technology with a proven
extraction of hydrocarbon liquid from natural gas, refinery track record in:
and petrochemical gas streams. Recovered liquid compo- – Refinery Off-Gas
– Petrochemical Off-Gas
nents can include ethylene, ethane, propylene, propane, – Natural Gas
isobutane as well as other valuable olefinic and paraffinic – Robust, adaptable and flexible design,
hydrocarbons. Combine your CRYO-PLUS™ plant with a and operation
Linde PSA to recover high purity hydrogen from refinery – Typical payout times of six (6) months
and petrochemical off-gas streams. to two (2) years

A member of The Linde Group

Linde Process Plants, Inc.
6100 South Yale Avenue, Suite 1200, Tulsa, Oklahoma 74136, USA
KPE
Phone: +1.918.477.1200, Fax: +1.918.477.1100, www.LPPUSA.com, e-mail: [email protected]
Select 81 at www.HydrocarbonProcessing.com/RS
 HPINNOVATIONS
SELECTED BY HYDROCARBON PROCESSING EDITORS

[email protected]

Siemens expands anaerobic- ence Recorder. This most recent (and free) proprietary FIBER FILM technology and
digestion product offering quarterly update enables the intrinsically caustic to remove acidic impurities during
Siemens Water Technologies has safe, hand-held field calibrator to graph and refining. Reducing high TAN (> 0.1 mg
acquired the JetMix hydraulic mixing sys- record average and differential pressure data. KOH/g) feed levels allows production of
tem from Liquid Dynamics Corp. This Now, the nVision (Fig. 1) can display, higher-quality and more-profitable prod-
proprietary system agitates sludge within record and graph differential pressure to a ucts from lower-grade and less-expensive
the anaerobic digestion process, optimizing remarkable accuracy of 0.025% of the dif- crudes. Other advantages of the NAPFIN-
digestion and methane production. The ferential reading up to 300 psi static, 0.05% ING HiTAN and FIBER FILM technolo-
latter can be captured and used as energy up to 3,000 psi static, and 0.1% up to gies are lower capital costs and a smaller
within a wastewater treatment facility. 10,000 psi static pressure. The nVision can plant footprint.
Compared to similar mixing systems, the also record 500,000 data points from each “NAPFINING HiTAN is another
JetMix system allows operators to schedule of its two modular sensors, simultaneously. practical example of the innovation that
mixing times—reducing power usage by It takes these measurements as frequently as is driving a transformed Merichem in ser-
60%–80% without decreasing gas produc- every 0.1 sec, without any change in accu- vice to an evolving refining industry,” said
tion or negatively affecting volatile solids racy between –20°C and 50°C.
reduction. Suitable for use in new instal- The nVision delivers this accuracy while
lations, as well as for retrofits or upgrades maintaining excellent field capability, and
for a variety of municipal and industrial without risking sensor damage. Other dif-
applications, the JetMix system comple- ferential calibrators sustain damage easily,
ments Siemens’ existing line of equipment when an improper connection or opera-
and solutions for anaerobic digestion. tion of valves exposes their single sensor
The JetMix system creates an effective to full static pressure. Because the nVision
mixing volume rating of 95% or more, Reference Recorder uses two independent
even with internal piping and roof support pressure modules, operators cannot damage
columns. The system uses powerful jets either sensor–providing they have selected
to maintain or resuspend solids. Nozzles the appropriate pressure modules for the
mounted inside the tank can be rotated anticipated static pressure.
360° to create a flow pattern that virtually “Our customers needed a reliable,
eliminates solids settling, reduces energy safe, and portable device for differential
requirements, and makes dead spots obso- measurements at high static pressure. The
lete. A top nozzle effectively controls scum nVision was already recording from two
and grease as well as foam and other floata- sensors with extraordinary accuracy across
bles. The modular design of the JetMix sys- a broad range of temperatures and pres-
tem allows for various pumps and nozzles sures. Measuring the difference between
to be used in combination to meet a wide the two was a logical step for us. However,
range of application requirements and load accurate differential pressure measurement
fluctuations. Viscosity, particle size, density, with two sensors was only possible because
settling rate and tank geometry are all con- of the arrow-straight linearity inherent in
sidered when designing the mixing system. our technology. At no additional cost, this
The mixing system can be paired with new capability puts tremendous value in FIG. 1 nVision differential pressure
thermophilic and mesophilic digesters, and the hands of our users.” said Tom Halacz- recorder.
can be coupled with heat exchangers. The kiewicz, president of Crystal Engineering.
system can be used in channels as well as Select 2 at www.HydrocarbonProcessing.com/RS
in circular, square and rectangular tanks. As HP editors, we hear about
Suitable applications include tanks with Next-generation technology new products, patents, software,
gas holders, or fixed and membrane roofs, removes high acidic impurities processes, services, etc., that are true
with the tanks located either above or Merichem Company, introduced NAP- industry innovations—a cut above
the typical product offerings. This
below ground. FINING HiTAN, a next-generation tech-
section enables us to highlight these
Select 1 at www.HydrocarbonProcessing.com/RS nology that removes high levels of naph-
significant developments. For more
thenic acid compounds in kerosine, jet information from these companies,
Accurate field calibrator fuel and diesel. NAPFINING HiTAN is please go to our website at
measures differential pressure based on Merichem’s popular, cost-effective www.HydrocarbonProcessing.com/rs
Crystal Engineering is releasing a sig- NAPFINING platform, and it employs and select the reader service number.
nificant addition to their nVision Refer- Merichem’s highly reliable and efficient
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 19
HPINNOVATIONS
Kenneth F. Currie, Merichem chairman ations. Baker Petrolite SULFIX additives pollution from SOx and H2S, improving
and CEO. reduce SOx air pollution that is created air quality and environmental compliance.”
NAPFINING HiTAN and NAPFIN- when hazardous hydrogen sulfide (H2S) Select 4 at www.HydrocarbonProcessing.com/RS
ING technologies employ the FIBER FILM is burned; helping US refiners meet the
contactor as a mass-transfer device and Environmental Protection Agency’s New Automation module
caustic as the treating reagent to remove Source Performance Standards (NSPS) for improves tank farm logistics
naphthenic acid compounds mainly from petroleum refineries. Building on years of experience and
jet fuel, kerosine and diesel, condensate and Refineries produce SOx emissions when technology in terminal and tank farm logis-
crude oil streams. H2S-laden gases are flared. This combus- tics operations, Emerson has added a move-
“NAPFINING HiTAN and FIBER tion process converts H2S to SOx. Now ment logistics management module to its
FILM are non-dispersive and extremely refineries can quickly reduce SOx emissions Syncade Smart Operation Management
reliable when compared with commercially by treating the flare gas with Baker Petrolite Suite. The new application complements
available treating alternatives. The smaller SULFIX additives to reduce the amount of Emerson’s established base of instrumenta-
footprint and smaller capital expenditure H2S it contains and avoid noncompliance tion, control and custody transfer systems
are attractive as well,” said Tom Varadi, vice issues without major capital investment. for tank farm and terminal product move-
president and general manager of Meri- Baker Hughes provides comprehensive ments. Initial installations include termi-
chem Process Technologies. “The onstream services for effective control of flare gas nals and tank farms in North America,
factor between routine turnarounds is H2S levels to help refiners select suitable Europe and Asia.
100%, whereas electrostatic precipitators additives, use the correct injection system Combining the power of the DeltaV
are much less reliable and incapable of pro- equipment and design, and implement an automation system with the Syncade
cessing high TAN feeds. appropriate monitoring program. suite’s operations management capabili-
Select 3 at www.HydrocarbonProcessing.com/RS “Baker Hughes has successfully applied ties, the new movement logistics manager
SULFIX additives and helped refinery cus- application supports marine, rail, truck
Additives reduce tomers reduce SOx emissions to comply and pipeline site operations. Key compo-
flare SOx emissions with environmental regulations,” notes Jerry nents include order management, logis-
Baker Hughes has developed additives Basconi, vice president and general man- tics planning and scheduling, inventory
specially designed to reduce sulfur oxide ager of industrial services of Baker Hughes. management, and production accounting.
(SOx) emissions from refinery flaring oper- “SULFIX products for flare gas reduce air It connects and interacts with every level

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KPE
20
I FEBRUARY 2011 HydrocarbonProcessing.com Select 154 at www.HydrocarbonProcessing.com/RS
Catalyst valve
problems?
We Have Solutions!
The Hemiwedge® Valve was designed to take on the severe conditions
of catalyst handling. If you thought there was no alternative to
traditional valve designs, we have great news!

The STATIONARY CORE in the Hemiwedge® Valve protects the

seating surfaces from the solids flow, resulting in greatly increased
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Tel: 936-539-5770 | Email: [email protected] KPE
Select 71 at www.HydrocarbonProcessing.com/RS
 A Better IEEE 841
Super-E® windings meet or exceed NEMA High strength cast iron frame, endplates,
Premium® efficiency standards conduit box and fan cover are designed
to reduce vibration and assure accurate
mounting dimensions

All internal rotor, stator

and shaft surfaces Oversize bearings on each end
are epoxy coated to for long life
prevent corrosion

Insulation system meets Inpro/Seal™ VBXX Bearing

requirements of NEMA Isolators at both ends assure
MG 1, Part 31.4.4.2 for protection from contamination
VFD use and considered
inverter-ready

Two-part epoxy primer Exclusive PLS® (Positive

inside and out, plus Lubrication System)
epoxy finish coat to assures proper bearing
prevent corrosion lubrication in all
mounting positions

All joints gasketed and sealed for added

Foot flatness within 0.005 inches for
protection against contaminant entry
precision alignment to driven equipment

Inside and Out

®
Baldor•Reliance 841XL severe duty motors are • Energy Efficient
engineered and built to meet or exceed the most rigid
severe duty service standards. You’ll find Baldor•Reliance
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©2010 Baldor Electric Company

KPE
Select 58 at www.HydrocarbonProcessing.com/RS
 HPINNOVATIONS
of the operation, from enterprise resource the compressor. The gastight compressor adviser for the project has worked closely
planning (ERP) systems to the devices that housing eliminates gas emission and losses with Golar LNG Limited on the develop-
load the ships and trucks and open the gate to the environment. ment of this project.
at the terminal. The system manages tasks The “Golar Freeze” was converted Laby-GI compressors are used for liquid
such as custody transfer of products, print- from an LNG carrier to an FSRU and is gas carriers, LNG/LPG FPSOs, FSRUs,
ing shipping documents and reporting capable of storing ~125,000 m3 of LNG LNG RVs and production platforms. They
final accounting results back to the ERP and delivering up to 480 million cubic are extremely reliable with unexcelled
for invoicing. feet per day (MMf3/d) of regasified LNG availability, combining best performance
“Today’s pressures on safety, security, to Dubai Supply Authority (DUSUP) for with unmatched operational flexibility and
cash flow and cost reduction require termi- further distribution into the Dubai natural long lifetime.
nal operations and tank farms in produc- gas network. Shell, as DUSUP’s appointed Select 6 at www.HydrocarbonProcessing.com/RS
tion facilities to be more reliable, repeat-
able, secure and safe,” said Jim Nyquist,
president of Emerson’s PlantWeb solutions
group. “These needs expand beyond phys-
ically controlling material movement to -YPLUKS`[V[OL
managing the business information associ-
ated with them. That’s why I’m proud that
Emerson can now offer our customers this
powerful, comprehensive solution.”
HQYLURQPHQW 
SHRSOHHUK`V\YI\KNL[
Automation can dramatically improve
tank farm and terminal efficiency, with
fewer people handling more activities and
doing it more reliably in less time. Adding
integrated order management and sched-
uling can help to increase the number of
trucks and ships handled by the facility.
Embedding the knowledge behind a paper-
driven process into an electronic system
also means the operation can do more with
less-experienced employees.
Select 5 at www.HydrocarbonProcessing.com/RS

Flue gas compressor

successfully commissioned
On December 10, 2010 Burckhardt
Compression successfully completed the Œ

mechanical test run of the Laby-GI com-

pressor. DNV certified the test run and
issued the survey report. The Laby-GI was
commissioned by Golar LNG Limited and
Burckhardt Compression on the floating
storage and regasification unit (FSRU)
“Golar Freeze”, which is now permanently
moored at the Jebel Ali port in Dubai. The
Laby-GI Compressor is used as a boil-off $VLQJOHVWHSGHFRQWDPLQDWLRQ
gas (BOG)/minimum send-out compres- IRUK\GURFDUERQSURFHVVLQJXQLWV
sor and has been successfully in operation
at full capacity. 6DIH ELRGHJUDGDEOH DQG FRPSDWLEOH ZLWK PHWDOOXUJ\ DQG ZDVWHZDWHU
The Laby-GI compressor is fully bal- V\VWHPV 7KH =\PH)ORZŠ 3URFHVV LV WKH LQGXVWU\ҋV PRVW FRPSOHWH
GHFRQWDPLQDWLRQ VROXWLRQ IRU UHÀQLQJ DQG SHWURFKHPLFDO DSSOLFDWLRQV
anced, eliminating unbalanced forces and
(IÀFLHQWDQGHIIHFWLYHLWVSDWHQWHGSURFHVVHOLPLQDWHVS\URSKRULFLURQ
moments guaranteeing a smooth operation
VXOÀGHVDQGUHPRYHVK\GURJHQVXOÀGHEHQ]HQHK\GURFDUERQVDQG
for all offshore applications. The unique
PRUH$ VLQJOH VWHS IRU D VROXWLRQ WKDWҋV KHDOWKLHU IRU WKH HQYLURQPHQW
design combines two well established seal-
DQG\RXUEXGJHW
ing technologies in a single crankgear for
lubricated or non-lubricated compression. 7HO_7ROO)UHH_]\PHÁRZFRP
Therefore, the Laby-GI compressor easily :RUOGZLGH/HDGHULQ5HÀQHU\'HFRQWDPLQDWLRQŒ
manages the compression of LNG BOG at
suction temperatures to -250°F (-170°C) Š
=\PH)ORZLVDPDUNRI8QLWHG/DERUDWRULHV,QWHUQDWLRQDO//&8QLWHG/DERUDWRULHV,QWHUQDWLRQDO$OO5LJKWV5HVHUYHG
without pre-heating the gas or pre-cooling
KPE
Select 155 at www.HydrocarbonProcessing.com/RS
23
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KPE
 HPIN CONSTRUCTION
HELEN MECHE, ASSOCIATE EDITOR

[email protected]

North America tion of a previously announced 50/50 man- ucts and services. Engineering work has
The Dow Chemical Co. plans to ufacturing joint venture to construct, own already begun, with hardware delivery to
increase ethane-cracking capabilities on the and operate a new membrane chlor-alkali begin in 2011.
US Gulf Coast over the next two to three facility located at Dow’s Freeport, Texas,
years, and improve these capabilities by integrated manufacturing complex. Europe
20%–30% in this timeframe. In addition, The new chlor-alkali facility is expected Technip has been awarded an engi-
Dow is also reviewing joint-venture options to begin operations in mid-2013, and will neering, procurement services and con-
for building a natural gas liquids (NGL) have a capacity of approximately 800 kilo- struction-management contract by Total
fractionator to secure this ethane supply. tons/yr. The new plant will create approxi- to increase hydrocracker capacity at the
Both actions are intended to capitalize mately 50 long-term jobs at the Freeport Normandy refinery located in Gonfreville,
on the favorable supply dynamics in North location, along with approximately 500 France. This project, which is part of a
America, and further bolster the competi- construction jobs. larger investment plan for the refinery, is
tive advantage of Dow’s plastics franchise, valued at more than €100 million (of which
as well as its high-margin, downstream per- South America Technip’s share is 20%).
formance businesses. Foster Wheeler AG’s Global Engineer- Technip’s scope includes debottle-
ing and Construction Group has been necking of the hydrocracking plant and
Alfa Laval has received an order for its awarded a basic engineering design and debottlenecking of the hydrogen unit
Packinox heat exchangers to be used in front-end engineering design (FEED) con- needed to operate the hydrocracker. This
what is said to be the world’s first full-scale tract for two grassroots refineries in Brazil extension will increase hydroconversion
integrated-gasification combined-cycle for Petrobras. The Premium I Refinery capacity to 10,000 tpd from the current
(IGCC) process for power generation with will be a dual-train, 600,000-bpsd facil- 8,000 tons, thereby enabling production of
carbon capture, which will be placed in the ity in Maranhao State, and the Premium more diesel fuel and kerosine.
US. The order value is about SEK 80 mil- II Refinery will be a single-train 300,000-
lion and delivery is scheduled for 2012. bpsd facility in Ceara State. Foster Wheeler BASF plans to expand its existing super-
The heat exchangers will be used in a will be the prime subcontractor to Honey- absorbent polymer-production capaci-
gas-treatment process of an IGCC power- well’s UOP, the managing process-technol- ties at its sites in Antwerp and Belgium,
generation plant. The project has received ogy licensor. The value of the contract was and at its Freeport, Texas, site. Gradual
funding from the US Department of not disclosed. debottlenecking and technical expansion
Energy and will, when finalized, include The contract includes basic design and measures are to raise annual capacity by
a state-of-the-art gasification facility with FEED for the main process units and aux- 70,000 tons to a total of 470,000 tons by
a capacity of more than 500 MW and an iliary units. 2012, with each site contributing an addi-
integrated carbon-capture facility. tional 35,000 tons
Petrobras has selected Emerson Pro-
Medicine Bow Fuel & Power LLC cess Management to provide process auto- A subsidiary of Foster Wheeler AG’s
has awarded Aker Solutions the front- mation technologies and services for the Global Engineering and Construction
end engineering and design (FEED) pack- Petrochemical Complex of Rio de Janeiro
age for its industrial gasification and liq- (Comperj) in Brazil. As the main automa- Trend analysis forecasting
uefaction plant located near the town of tion contractor for Comperj, Emerson will Hydrocarbon Processing maintains an
Medicine Bow, Wyoming. Aker Solutions deliver engineering services and technolo- extensive database of historical HPI proj-
successfully completed a pre-FEED study gies for integration of the refining unit’s pro- ect information. The Boxscore Database is a
35-year compilation of projects by type, oper-
for the project in July 2010. Since then, cess automation and systems, and selected ating company, licensor, engineering/construc-
Aker Solutions has worked under a letter of project utilities and offsite operations. tor, location, etc. Many companies use the his-
intent to provide services relating to design Built on an area of 45 million m2, the torical data for trending or sales forecasting.
review and licensor support, as well as addi- Comperj complex will be able to process The historical information is available in
comma-delimited or Excel® and can be custom
tional pre-EPC engineering and design. 165,000 bpd of heavy crude when its first sorted to suit your needs. The cost depends on
The facility will produce liquid transport refining unit begins operations in 2013, the size and complexity of the sort requested.
fuels and is due to come online in 2015. and the same amount in a second unit is You can focus on a narrow request, such as
When complete, the plant will convert coal expected five years later. In addition to sys- the history of a particular type of project, or
you can obtain the entire 35-year Boxscore
into up to 21,000 bpd of gasoline and liq- tems for process control, safety, fire and database or portions thereof. Simply send
uefied petroleum gas (LPG) liquid fuels. gas detection, machinery monitoring, and a clear description of the data needed and
management of process and maintenance receive a prompt cost quotation.
The Dow Chemical Co. has announced information, Emerson will also supply Contact: Drew Combs
that Dow and Mitsui & Co., Ltd., of measurement instruments, control valves, P.O. Box 2608, Houston, Texas, 77252-2608
713-520-4409 • [email protected]
Tokyo, Japan, have completed the forma- pressure regulators, and other related prod-
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 25
HPIN CONSTRUCTION
Group has been awarded a contract by engineering activities will be completed by ery will be integrated at the Petkim pet-
Kuwait Petroleum International Lubri- mid-2011. rochemicals site on the Aegean coast.
cants to provide detailed engineering ser- As PMC for the SOCAR and TURCAS
vices for a brown-field lube-oil blending The State Oil Co. of the Azerbaijan Aegean Refinery (STAR) project, Fluor will
plant to be built at Kuwait Petroleum’s Republic (SOCAR) and TURCAS Rafi- assist STRAS in selecting and managing the
facility in Antwerp, Belgium. neri A.S. (STRAS), the joint venture engineering, procurement and construction
The lube-oil blending plant will sub- of SOCAR and TURCAS Petrol A.S. (EPC) contractor(s) and provide overall
stantially enhance the Antwerp facility’s (TRCAS), have awarded Fluor Corp. a project and construction management.
ability to operate at European scale by project-management consultant (PMC) Project work is underway, with the
increasing production capacity from 125 contract for a new refinery to be built in start of site preparation. EPC work is esti-
million lpy to 250 million lpy. The detailed Aliaga, Turkey. The new planned refin- mated to be in mid-2011, and construction
startup is scheduled to begin in the first
quarter of 2012.

Africa
Paratherm Technip has been awarded a contract
by Sonatrach, the Algerian national oil
GLT™ Synthetic company, for refurbishment and revamp-
ing of the Algiers refinery. This lump-sum

Heat Transfer Fluid turnkey contract, worth approximately

$908 million, will last 38 months and
cover the execution of the complete scope
showed 30% less of works, including the design, supply of
equipment and bulk material, construction
degradation than and startup.
The revamp of the existing installations
a widely used will enable refining capacity to be increased
from 2.7 million tpy to 3.6 million tpy.
Synthetic Heat The new units will allow the refinery to
produce gasoline at specifications similar to

Transfer Fluid. those in force in Europe. This project will

be carried out by Technip’s operating center
in Paris, France.

Middle East
Petroleum Development Oman
(PDO) has awarded a seven-year engi-
neering and maintenance services contract
(EMC) to Wood Group–CCC, a joint
Degradation in heat transfer fluid can Immersion Engineering™™ Services venture set up to provide operations and
cause a multitude of problems from loss of Fluid Analysis maintenance services for the oil and gas
production efficiency to unplanned system Fluid Maintenance and petrochemical industries in Oman,
Training
shutdown. According to the ASTM D6743 Troubleshooting Bahrain, Kuwait, Qatar, Saudi Arabia,
standard test method for thermal stability Consulting UAE and Yemen. The contract, which
of organic heat transfer fluids, at 600°F for has a three-year extension option, will
500 hours Paratherm GLT Heat Transfer Products include integrated engineering, construc-
Fluid created 30% less product degradation Paratherm MG™ HTF Paratherm SC® Cleaner tion, maintenance and support services for
than a widely used comparable alternative. Paratherm HR™ HTF Paratherm LC™ Cleaner
Paratherm GLT™ HTF Paratherm AC™ Cleaner
existing PDO facilities onshore in South-
Additionally, Paratherm GLT Fluid is
compatible for top-off with similar synthetics
ern Oman.
and is near colorless versus other yellowish
colored fluids which show signs of impurities Shell Global Solutions International
that may contribute to degradation. B.V. has signed three license agreements
Go to our website or call one of our with the state-owned North Refineries
HEAT TRANSFER FLUIDS
Immersion Engineering™ team for more Co. of Iraq, in Kirkuk, Northern Iraq.
4 Portland Road
details and special services. All it takes West Conshohocken PA 19428 USA Shell Global Solutions will provide a pro-
is a short conversation with one of our cess license and basic-engineering pack-
800-222-3611
®

sales engineers to greatly eliminate the 610-941-4900 • Fax: 610-941-9191 ® age for a kerosine hydrotreater, a diesel
risk of degradation in your system. [email protected] hydrotreater and a vacuum gasoil (VGO)
Contact us today. www.paratherm.com
hydrocracker unit as part of the agree-
ment. Each agreement includes the grant
KPE
Select 156 at www.HydrocarbonProcessing.com/RS
26
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HPIN CONSTRUCTION
of a license to Shell proprietary technology Asia-Pacific
and the provision of engineering services. CB&I has announced that Lummus Jacobs Engineering Group Inc. has
Agreements for the supply of catalysts Technology has been awarded a contract received a contract from CPC Corp.,
and reactor internals are expected to be by Liaoning Tongyi Petrochemical Co., Taiwan, to design and license Jacobs’ pro-
signed in the future as part of the deal. Ltd., for the license and engineering design prietary EUROCLAUS technology for a
Based on Shell’s experience as both an of grassroots olefins-conversion technology desulfurization unit as part of the Ta-Lin
owner and an operator, these licensed (OCT) units and CATOFIN dehydroge- refinery expansion project in Kaoshiung,
technologies are likely to provide North nation units at several of its sites in the Taiwan.
Refineries Co. with an integrated solution People’s Republic of China. The units will This project is said to be the first to
that will help optimize the new refinery’s produce 684,000 metric tpy of isobutylene combine Jacobs’ EUROCLAUS technol-
operations. and 950,000 metric tpy of propylene. ogy with DynaWave technology, which
is engineered and licensed by US-based
MECS, Inc. The combination of these
two unique technologies reportedly
makes it possible to achieve very-low-
sulfur emissions at low-investment cost
compared to existing technologies. The
new desulfurization unit will be inte-
gral to CPC’s refinery operations. CPC
will design and build the Ta-Lin refinery
expansion. The new facility, scheduled
to be operational in 2013, will produce
clean-fuel products for the local Taiwan-
ese market.

The Shaw Group Inc. has been

selected by GAIL (India) Ltd. to provide
its proprietary technology and basic engi-
neering for a new 450,000-tpy ethylene
plant. Shaw will also provide support dur-
ing detailed engineering, procurement
and construction, and commissioning and
startup of the plant, which will be part of
GAIL’s petrochemical complex in Pata,
Uttar Pradesh, India.
Energy conservation and optimization are key issues for process plant The undisclosed value of the contract
profitability and regulatory compliance. Proper evaluation and correction was included in Shaw’s Energy & Chemi-
of energy losses can help bring significant cost savings and reduce cals segment’s backlog of unfilled orders in
greenhouse gas emissions. the first quarter of fiscal year 2011.

Our complete optimization program can help you: Stamicarbon, the licensing and intel-
lectual property center of Maire Tecni-
■ Evaluate opportunities for energy savings
mont S.p.A., has signed a license agree-
■ Develop AFE capital cost estimates ment with Inner Mongolia Bodashidi
■ Provide ROI calculations for management review Co., Ltd., in the People’s Republic of
■ Identify needed operation and procedure changes China (PRC) for a urea plant with a capac-
■ Perform front-end studies ity of 2,860 metric tpd. The plant will be
■ Integrate data for air emissions compliance built in the Industrial Zone of Nalinriver,
■ Implement advanced process control Wushen, Inner Mongolia, PRC. The urea
plant will use the Stamicarbon Urea2000P-
Contact us today for information on how Mustang can help reduce the lus pool condenser technology.
energy stranglehold on your facility. Stamicarbon will deliver the process
design package (PDP) and associated ser-
vices. The plant will be built by Wuhuan
Engineering Corp. of China as the sub-
contractor of China Chemical Engi-
Email: [email protected] neering Second Construction Group.
www.mustangeng.com Wuhuan has been chosen by the customer
as the designated EPC contractor. Startup
is planned in 2013. HP
KPE
Select 157 at www.HydrocarbonProcessing.com/RS
28
 KNOW-HOW DELIVERED
We put tested refining technologies
and processes to work in your
world. From hydroprocessing to
fluid catalytic cracking and
Veba Combi-Cracking to resid processing, we offer
proven know-how. So you can improve productivity and
lives. KBR Technology licenses deliver for greenfield
and existing refineries of virtually every type and size.
See HOW we can help you meet mission-critical goals.
Click refining.kbr.com/HP

REFINING

© 2011 KBR
All Rights Reserved
K11003 2/11 KPE
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 KPE
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 HPI CONSTRUCTION BOXSCORE UPDATE
Company City Plant Site Project Capacity Unit Cost Status Yr Cmpl Licensor Engineering Constructor
AFRICA
Algeria Naftec Spa Skikda Skikda BTX RE None U 2012 GTC, Inc GTC, Inc
Libya Harouge Oil Operation Ras Lanuf Ras Lanuf Storage, Oil None 63 U 2012 Punj Lloyd Ltd Punj Lloyd Ltd Punj Lloyd Ltd
Morocco OCP Jorf Lasfar Jorf Lasfar DAP (4) EX None P 2013 Jacobs Engineering SA Jacobs Engineering SA Jacobs Engineering SA

ASIA/PACIFIC
China CNOOC Dongfang Dongfang Refinery None 12 U 2013
India Rashtriya Chemicals Thal Vaishet Thal Vaishet Ammonia RE bbl U 2011 Haldor Topsøe PDIL
South Korea Hyundai Petrochem Co Ltd Daesan Daesan Aromatics Extraction Mtpy E 2011 HRI KBR|HEC HEC
Taiwan Chinese Petroleum Corp Kaohsiung Kaohsiung Diesel, HDS (2) 50 Mbpd 34.6 A 2010 Axens Fu-Tai Engr Fu-Tai Engr
Thailand Map Ta Phut Olefins Map Ta Phut Map Ta Phut Aromatics Complex TO 600 Mtpy C 2010 GTC, Inc

EUROPE
Greece Hellenic Petroleum SA Thessaloniki Thessaloniki Naphta 2600 bpsd 184 U 2011
Italy Montedipe SpA Porto Marghera Porto Marghera Aromatics Extraction 400 Mtpy U 2012 Montedipe Tecnimont Tecnimont
Kazakhstan AGIP KCO Kashagan Kashagan Field FPSO 150 kbpd 30000 E 2012 KBR
Romania Petrochemical Holding AG Onesti Onesti Paraxylene 400 Mm-tpy P 2012 GTC, Inc
Russian
Federation Lukoil Perm Perm Aromatics Complex RE 320 Mtpy E 2011 GTC, Inc

LATIN AMERICA
Colombia Ecopetrol Barrancabermeja Barrancabermeja FCC Gasoline RE bbl 30 P UOP AltairStrickland
Cuba PDVSA Matanzas Matanzas Refinery, Heavy Ends 150 bpd 4300 P 2015
Ecuador Refineria del Pacifico-CEM El Aromo El Aromo Refinery 300 bpd 12500 P 2013 PGN
Mexico Petroleos Mexicanos Cangrejera Cangrejera Styrene EX 100 Mtpy H

MIDDLE EAST
Iran Esfahan Oil Refinery Co Esfahan Esfahan Isomerization 27 Mbpsd 187 E 2011 UOP Namvaran|HEC Dorriz
Qatar Qatar Shell GTL Ltd Ras Laffan Ras Laffan MEG 1.5 m-tpy P
Saudi Arabia SAMREF Yanbu Yanbu Clean Fuels None 200 F 2013

UNITED STATES
California Valero Refining Co Benicia Benicia FCC Gasoline RE bbl 5 U 2011 AltairStrickland
Georgia CARBO Toomsboro Toomsboro Proppant resin None P
Montana ExxonMobil Billings Billings FCC Gasoline RE bbl 8 P AltairStrickland
Ohio Marathon Oil Canton Canton FCC Gasoline RE bbl P AltairStrickland
Oklahoma ConocoPhillips Ardmore Billings Coker, Delayed RE bbl 8 P AltairStrickland
Texas LyondellBasell Industries Houston Houston Coker, Delayed RE bbl 12 P 2013 FW FW AltairStrickland
Utah Holly Corp Woods Cross Woods Cross Benzene Reduction None E 2011 GTC, Inc
Wyoming Medicine Bow Fuel Medicine Bow Medicine Bow Gasification and Liquefaction 21000 bpd F 2015 Aker Solutions

See http://www.HydrocarbonProcessing.com/bxsymbols for licensor, engineering and construction companies’ abbreviations,

along with the complete update of the HPI Construction Boxscore.

BOXSCORE DATABASE ONLINE

THE GLOBAL SOURCE
FOR TRACKING HPI
CONSTRUCTION ACTIVITY
For more than 50 years, Hydrocarbon Processing
magazine remains the only source that collects and
maintains data specifically for the HPI community,
publishing up-to-the-minute construction projects
from around the globe with our online product,
Boxscore Database. Updated weekly, our database
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For a Free 2 -Week Trial, contact Lee Nichols at
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HYDROCARBON PROCESSING FEBRUARY 2011
I 31
When the right reaction matters ...

The petroleum refining landscape is constantly evolving through changing crude slates, shifts in
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KPE
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 HPI VIEWPOINT

Consumer protection is a key issue for E15

NPRA wants to be sure that adding greater amounts of ethanol to gasoline
is safe and will not cause engine damage

NPRA is not anti-ethanol—our members blend it with gasoline

Charles T. Drevna is the president of the
every day to manufacture the E10 fuel that safely powers most US
National Petrochemical & Refiners Associa-
tion (NPRA), a national trade association with
vehicles. We simply want to be sure that adding greater amounts
more than 450 members, including those of ethanol to gasoline is safe and will not cause engine damage.
who own or operate virtually all US refining Following the old proverb to “look before you leap,” we believe
capacity and most all petrochemical manu- that learning more about E15 before approving its use is just
facturers in the US. Prior to his election as common sense.
president in 2007, Mr. Drevna served as Because of our concern with consumer protection, NPRA has
NPRA’s executive vice president and director filed a lawsuit asking a US appeals court to overturn what we believe
of policy and planning. Mr. Drevna has an extensive background in
was the EPA’s premature and unwise decision to approve the use
energy, environmental and natural resource matters, with more than
36 years of broad energy industry experience in legislative, regulatory,
of E15 in cars and light trucks for the 2007 and later model years.
public policy and marketplace issues. Prior to joining NPRA, Mr. Drevna
served as director of state and federal government relations for Tosco, Misfueling. Based on experience with leaded and unleaded
Inc., the nation’s largest independent petroleum refiner, where he was gasoline years ago, we know that millions of consumers would no
responsible for liaison with Congress, federal regulatory agencies and doubt use the wrong fuel for the wrong vehicle—a problem called
state governments. Mr. Drevna also served as director of government misfueling—if E15 becomes widely available.
and regulatory affairs for the Oxygenated Fuels Association, where No matter what warning signs the EPA requires gasoline retail-
he held similar responsibilities, and as vice president at Jefferson
ers to post at their pumps, many consumers would undoubtedly
Waterman International, a Washington, DC-based consulting group
where he specialized in domestic and international energy issues. Mr.
pump E15 into older cars and trucks and use it in outdoor power
Drevna also served as vice president of public affairs at the Sun Coal equipment, motorcycles, boats and snowmobiles.
Co., a Knoxville, Tennessee-based unit of Sun Co., Inc. (Sunoco), and Some of this misfueling would be unintentional—consum-
with the parent company as manager of public policy at its corporate ers not paying attention to warning labels on pumps when they
headquarters in Philadelphia. Mr. Drevna has a significant background drive up in their older vehicles, or filling gasoline cans to run their
in environmental management that includes service as director of lawnmowers and chain saws after they fill up their cars without
environmental affairs for the National Coal Association in Washing- going to a different pump.
ton, DC, and as supervisor of environmental quality control for the
Some misfueling would be deliberate because E15 may be
Consolidation Coal Co. in Pittsburgh. He received his BA in chemistry
from Washington and Jefferson College and performed graduate
slightly cheaper than E10 gasoline at times, due to variability in
work at Carnegie-Mellon University. the price of oil. Many consumers would not realize that ethanol
packs less energy than gasoline and, hence, gives them lower mile-
age, canceling out the value of a slightly lower price.
Americans have long counted on our nation’s petroleum refin- The EPA’s decision threatens consumer safety in numerous
eries to provide them with safe, affordable, efficient and reliable ways, even if we assume—and we do not—that testing has proven
gasoline and diesel fuel for their vehicles and outdoor power conclusively that E15 is safe for cars and light trucks from 2007
equipment. and later model years.
Unfortunately, a decision last October by the US Environ- Misfueling could cause costly damages to all sorts of gasoline
mental Protection Agency (EPA) to authorize the sale of gasoline engines. Snowmobile engines could conk out in the middle of the
containing 15% ethanol (E15) for late-model vehicles—up from frozen wilderness, and boat engines could fail in the middle of the
the current limit of 10% ethanol (E10)—could reduce the safety ocean—stranding people in life-threatening conditions. Chain
of the gasoline Americans rely on. saws could overheat and run when their operators wanted to turn
Concern about the potential safety threat of a 50% increase in them off, endangering operator safety.
the amount of ethanol in gasoline motivated many refiners and NPRA members don’t want the gasoline they manufacture to
the National Petrochemical & Refiners Association (NPRA), to cause these kinds of problems for consumers. Like any manufac-
call on the EPA to conduct thorough and objective scientific tests turer, refiners know the truth of the Ford Motor Co. slogan of the
on the impact of E15 on gasoline engines before authorizing use 1990s—“quality is job one.” And no element of quality is more
of the fuel. important than safety.
Unfortunately, the EPA rejected our call and decided to rush to Refiners are concerned that if E15 causes engine problems—
judgment, under pressure from the ethanol industry. As a result, particularly those that lead to injuries or worse for consumers—a
we believe the EPA decision approving E15 for limited use was a wave of class-action liability lawsuits could follow, seeking billions
disservice to the American consumer. of dollars in damages.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 33
HPI VIEWPOINT
■ In early January, NPRA filed suit along EPA engaged in to cut corners to approve the use of E15 before
its use has been justified by scientific testing.
with the International Liquid Terminals For example:
• The Clean Air Act clearly requires that any group petitioning
Association and the Western States the EPA for a waiver to change the blend of ethanol in gasoline
provide all the information necessary to approve the waiver. But
Petroleum Association, asking a federal Growth Energy—the ethanol industry group seeking the E15
waiver—failed to do this, since substantial additional testing by
appeals court to overturn the EPA’s deci- the EPA and the US Department of Energy (DOE) was required.
We believe yet more testing and evaluation of data is needed.
sion to approve the use of E15 for late- • The EPA based its E15 partial-waiver decision on studies
submitted to the public rulemaking docket on the day before the
model vehicles. US automakers and engine EPA announced the partial waiver, providing no time for stake-
holder review or meaningful public comment on crucial informa-
manufacturers have filed similar lawsuits. tion used to justify the approval of E15. The EPA’s partial-waiver
Significantly, the ethanol industry has refused to accept liability decision was based almost entirely on data submitted to the record
for engine damage that could be caused by E15. Ethanol produc- after the public comment period closed in 2009. We believe this
ers are happy to profit from E15, but leave it to refiners, retailers is a violation of the Administrative Procedures Act.
and others to remain liable for any damages that E15 might cause. These irregularities are important—not just minor technicalities.
The good news for consumers is that the EPA’s decision does If the EPA or any federal agency is allowed to operate outside
not require refiners or retailers to blend or sell E15 and does not the constraints of the law, a dangerous precedent would be set,
require consumers to buy the fuel. Based on initial opposition to usurping the power of our elected representatives in Congress to
E15—not just from refiners and retailers, but also from the auto, pass laws limiting the powers of the executive branch of govern-
boat, snowmobile and outdoor power equipment industries—it ment. This would open up a Pandora’s box of problems in the
is not likely that E15 will become widely available anytime soon. future, no matter who is president and no matter what political
Nevertheless, NPRA is concerned about harm that E15 could party is in power at any given time.
cause to American consumers should it come into widespread use We believe testing of E15 should continue and be broadened
without adequate testing. to determine which engines—if any—can safely use the higher
We are also concerned about procedural irregularities that the ethanol blend.

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HPI VIEWPOINT
Things not tested for. DOE testing of E15 simply looked • Evaporative emissions from fuel leaks and permeation, such
at the ability of the pollution control equipment of some cars to as vapors leaking out of an idle car with the engine off and parked
stand up to E15. The DOE did not conduct needed testing to outside on a hot and sunny day.
determine the impact of E15 on: Extensive testing in all of these areas is well underway—with
• Engine durability the knowledge of both the EPA and DOE—by the privately
• Tolerance of the check-engine light funded Coordinating Research Council. However, those tests
• Durability of other components, such as the fuel pump and require more time for completion.
the fuel level sensor Many issues of public policy are remote and don’t directly affect
the majority of Americans. The fate of E15 is not one of these.
The US Department of Transportation estimates there are
UPCOMING NPRA EVENTS: about 255 million cars and passenger trucks on the road in the
(more information at www.npra.org) US. Millions of Americans own boats, motorcycles, snowmobiles,
lawnmowers, chain saws, and other products that run on gasoline.
Security Conference So the safety of E15 is an issue that directly affects just about every
March 1–2, 2011 American family.
Houston, Texas The EPA is being sued by a broad range of organizations that
object to its E15 decision on a number of grounds. These include
Environmental Committee claims by the food industry that using more ethanol in gasoline
would drive up corn prices and thus raise the price of many food
Spring Meeting
items, and claims by environmentalists that expanded ethanol
March 8–9, 2011 production and use would harm the environment.
Washington, DC We trust the courts will give the issue of E15 the serious con-
sideration it deserves.
Annual Meeting NPRA believes that, right now, there are just too many unan-
swered questions about E15 to allow approval of its use. Instead
March 20–22, 2011
of asking the American people to pump first and ask questions
San Antonio, Texas later, the EPA should get more answers first to the many questions
remaining about the safety of E15. HP

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36
 CLEAN FUELS SPECIALREPORT

Slurry-phase hydrocracking—
possible solution to refining margins
Opportunity crudes require more hydrogen addition to upgrade
orphan product streams into higher-value ‘clean’ products
M. MOTAGHI, B. ULRICH and A. SUBRAMANIAN, KBR Technology, Houston, Texas

R
efinery margins are complex topic; margins are subject to crudes entering the market place are substantially heavier than
substantial uncertainties and are impacted by global fluc- the current crude basket. This is evident by the decreasing API
tuations in regional feed and product pricing structures. as shown in Fig. 1, of the composite worldwide crude blend and
A conscientious analysis of historical data will indicate that for increasing volumes of extra-heavy crudes such as Canadian and
every one good year, on average, refiners are subject to seven years Latin American bitumens.
of depressed margins. New globalization trends, which include a As the world’s supply of crude oil becomes heavier and con-
changing transport-fuel supply/demand balance, geographic shift tains higher sulfur levels, the challenge to the refiners will be
in consumption, soaring crude-oil prices, depressed natural-gas compounded by the need to meet the growing demand for light,
prices and impending regulations, all pose interesting challenges high-quality, ultra-low-sulfur transportation fuels. This leads to
to the very survival of many small- and medium-sized refineries. the next major determining factor that sets refinery margins, i.e.,
quality of products.
Definitions of profitability. A simple analysis of refin-
ery economics will reveal that margins are largely impacted by Product quality. Global trends show a growing diesel demand
three basic factors; crude cost, type of products produced and and stable-to-declining gasoline demand (Fig 2). As the world
disposition of low-value, stranded streams. While the first two emerges from the global recession and as the growth margin in
factors are simple to understand, the relationship between the 40% of the world’s population continues at a rapid pace, this
refiner’s ability to handle these orphaned streams and margins trend can only be expected to amplify. With the majority of exist-
is more complex. ing refinery configurations slanted towards gasoline production,
the price differential between diesel and gasoline will widen over
Crude price. The cost of crude is the single most important fac- the long haul, validating the market tilt towards dieselization.
tor in setting refinery margins. This is the primary reason for the In addition, regulatory demands will only accelerate the shift
recent surge in refinery upgrades targeted at processing “opportu- towards lower density, higher-cetane index, ultra-low-sulfur die-
nity crudes.” While the definition of opportunity crudes is nimble
and can vary from refinery to refinery, for the purpose of this 34 1.3
article, it makes sense to simply define these crudes as the cheap-
est possible crude basket available to any given refinery on any
given day. This basket may consist of heavy or extra heavy crudes,
bitumen-derived crudes, high-acid/high-metals naphthenic crudes
or high metals-containing, paraffinic, heavy inland crudes.
Most refiners are limited in their ability to handle this wide
API gravity

Sulfur, %

range of opportunity crudes; more often than not, they are con-
strained by the residues derived from these crudes. In recent 33 1.2
years, the surge in interest over resid upgraders was catalyzed by
the growing light-heavy differentials. This, in turn, forced refin-
ers to evaluate their bottoms processing technologies, as margins
dictated a higher percentage of heavy oils in their crude diet.
Although the large light-heavy differentials have since diminished,
this phenomenon is likely to be temporary. The renewed inter-
est in monetizing heavy-oil reserves and the influx of substantial 32 1.1
heavy crude volumes to the marketplace suggests that in the long 1990 1995 2000 2005 2010 2015 2020 2025
Global petroleum outlook
run, refinery margins are likely to return, in large part influenced
by the restoration of the light-heavy differentials. Central to this FIG. 1 Crude API trends, 1990–2025.
theory is that light-oil fields are on the decline and almost all new
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 37
SPECIALREPORT CLEAN FUELS

sel production, as the regional outlets for lower quality transport try to take on the burden of these operating facilities. Regulatory
fuels diminish. trends are almost always unidirectional, and the shipping industry
This combination of lower cost “opportunity crudes” and the can only expect the sulfur oxide (SOx) regulations to extend to
need to produce high-quality distillate-selective products is an nitrogen oxide (NOx), particulates, volatiles and other controls,
important consideration for refiners, when making long-term, not to mention the added capital investment, operating cost,
high-dollar investment decisions. monitoring and reporting requirements. Conversely, the refining
industry is unlikely to invest in expensive VR hydroprocessing
Choices. The least understood variable in determining refin- with the sole purpose of producing specification bunker fuels.
ery margins is the disposition of stranded streams. Refineries
are littered with low-value streams that are blended off, often Regulation directs actions. The global trends show a sharp
downgrading higher-value products for the sole purpose of decline in high-sulfur fuel oil demand (Fig. 4), driven mainly by
finding positive outlets for less saleable streams. While the abil- environmental regulations. While the sharp decline in fuel oil
ity to upgrade these streams is a major factor that sets refinery prices seen through the mid part of this decade has been tempo-
complexity, the solutions for these streams often rests in under- rarily arrested by the installation of many cokers, a reversal can be
standing its potential applications and value within and outside expected as regulatory pressures extend to the rest of the world. As is
the refining industry. evident from the crack margins, producing large volumes of fuel oil
The single largest stranded stream for most refineries is the will result in negative refinery economics and cannot be sustained.
vacuum residue (VR). The bulk of the operating refineries around Road asphalt is a relatively small market (Fig. 5), and envi-
the world have little or no residuum processing capability and ronmental pressures are also likely to force refiners to produce
produce large volumes of high-sulfur fuel oil and bunker fuel. A specification-grade bitumens without resorting to air blowing.
small volume is used to produce road asphalt. The future of VR While this may lead to investment in alternate technologies such
is, therefore, intrinsically tied to the future of these three outlets. as solvent de-asphalting, the overall impact on the volume of
The large growth market for residues may appear to be the stranded VR or its pricing, will be minimal.
bunker fuel market predominantly influenced by globalization All of these factors lead to one obvious conclusion. Going
trends and consequential incremental trade and shipping traffic. forward, high refining margins will depend upon the ability to
However, the use of VR as the major blending component in capitalize on opportunity crudes, while consistently producing
bunker fuel will come under serious scrutiny as new maritime high-quality distillate-selective products from refinery residues.
regulations come in to effect starting in 2015 (Fig. 3). This will Selecting the appropriate residue upgrading technology, therefore,
significantly inhibit VR demands, and the eventual solution may is a critical part of this puzzle that will define the future of refining
come from either the shipping or the refining industry. and refinery margins.
While one of the solutions under debate involves using
onboard flue gas scrubbers, this issue is more complex. There are Selecting residue upgrading technologies. To better
several reasons to underscore the reluctance of the shipping indus- understand the technology options, one must recognize that VR,
in essence, is defined by what is not VR. The quality and quan-
tity of VR is a function of crude selection and the lowest boiling
35
Diesel impurity contained within the resid fraction that shows up as the
30
limiting factor in the vacuum gasoil (VGO) fraction that is fed to
Price projection

25 a catalytic hydrotreater, hydrocracker or fluid catalytic cracking

20 Gasoline (FCC) process. The choice of resid conversion technology must
15 be set by project economics, preferred reaction chemistry and
10 mechanism of conversion aimed at reliably achieving the overall
5 processing objectives.
0 We present seven questions that one would expect refiners to
1990 1995 2000 2005 2010 2015 2020 ponder as they investigate the appropriateness of available tech-
nology options. The direct relevance of these questions is premised
FIG. 2 Demand for gasoline and diesel, 1990–2010.
on projected market trends and is intended to address the desire
to achieve and sustain high refinery margins:

5
Possible delay until 2025 12
Fuel oil demand, million bpd
Sulfur maxium content, %

4 10 Western hemisphere
Eastern hemisphere
3 Global 8
ECA 6
2
4
1 2 Source: Purvin & Gertz
0 0
2005 2010 2015 2020 2025 2030 1990 1995 2000 2005 2010 2015 2020 2025

FIG. 3 Expected timeline for IMO regulation enactment. FIG. 4 Declining oil demand trend, 1990–2015.

KPE
38
I FEBRUARY 2011 HydrocarbonProcessing.com
 CLEAN FUELS SPECIALREPORT

1. Has the technology been demonstrated in one or more weighed against the prevalent market conditions of the past, the
large scale units? conclusions are obvious.
2. Can the technology handle residues irrespective of the feed However, going forward, with projected high crude oil prices,
quality? low natural gas prices and diminishing outlets for low-grade
3. Can the technology achieve near complete conversion on petroleum coke, the need for hydrogen addition is now here. In
a once-through basis? the rest of this article, we will examine the landscape of the avail-
4. Can the technology produce finished diesel-selective products? able resid upgrading hydrogen addition technologies against this
5. Does the technology database demonstrate the ability to backdrop. As shown in Fig. 6, the technology choice for resid
handle a whole range of crudes?
6. Can the technology do all of this with high reliability?
20
7. Can the technology achieve all of this at an attractive net
present value (NPV)? 18 Thermal processing or slurry phase
Aided by low crude oil prices and high natural gas prices, the 16
delayed coker has, thus far, been the technology of choice for resid
upgrading. When tested against the “seven questions” above, and 14

Conradson carbon, %
Ebullated bed or slurry-phase
12
Demand for asphalt, million bpd

2.5 10
Western Hemisphere
2.0 8
Eastern Hemisphere Resid FCC
1.5 6

1.0 4

0.5 2
Source: Purvin & Gertz Fixed-bed hydrocracker
0.0 0
1 10 100 1,000 10,000
1990 1995 2000 2005 2010 2015 2020 2025 Metals content, Ni + V ppm

FIG. 5 Demand for asphalt for road and roofing applications, FIG. 6 Resid upgrading technology options as directed by CCR %.
1990–2025.

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HYDROCARBON PROCESSING FEBRUARY 2011
I 39
SPECIALREPORT CLEAN FUELS

make the process capital intensive with lim-

Vacuum ited overall benefits.
residue
1st stg. Hot 2nd stg.
To improve the economics of fixed-
Offgases
reactor separator reactor sulfur etc. bed resid hydrocrackers, the unit must
be protected from feed impurities. A feed
Gas cleanup unit such as a solvent deasphalter
Recycle gas (SDA) may be installed upstream of the
compressor cleaning
Additive hydrocracker to reject the heaviest CCR and
Cold
separator C4 metals containing fraction as a pitch stream.
The SDA works on the principles of
Vacuum Naphtha solubility driven separation and is capable
H2 column of lifting light deasphalted oil (DAO) from
Middle
Makeup distillate resid feeds. For most crudes, especially the
compressor Fractionator lower value opportunity crudes, the over-
Residue all lift will be low, limited by the CCR
VGO
and metal specifications set by the DAO
FIG. 7 Typical resid hydrocracker flowsheet. hydrotreating catalyst.
As a result of the low DAO yield, the
reject asphaltenic stream will be large and
can range from 50 wt%–80 wt% of the VR.
hydroprocessing is inherently determined by the metals and Con- For refiners who lack an economic outlet for this pitch stream, the
radson Carbon Residue (CCR) content in the residuum. value derived from the incremental distillate production through
hydroconversion of the DAO is negated by transportation and
Fixed-bed resid hydrocrackers. Fixed-bed technologies handling costs associated with moving the pitch from the facility.
have been used to hydrotreat residues containing low concentra- Thus, DAO derived from the vast majority of solvent deasphalters
tions of metals and CCR. In most cases, the operation of these operating in fuel services is directed to an FCC unit.
units is severely inhibited by the rapid deactivation of the catalyst Fixed-bed resid hydroconversion processes will achieve mini-
system. The resultant combination of high operating pressure, low mal overall resid conversion, will produce a large volume of fuel
conversion, poor quality products and low catalyst cycle length oil, and are inherently limited by changing feed qualities. This
incompatibility is evidenced by high operating pressures, large
capital investments, low catalyst cycle length and a maintenance-
intensive operating history. The quality of the products will not
meet Euro V specifications, and the overall investment will not
be commensurate with the derived benefits. When tested against
the “seven questions to ponder,” it is obvious that fixed-bed resid
hydrocracking technology based schemes would need to be criti-
cally examined by the refiner on almost every issue.

Ebullated-bed hydrocrackers. Another option that has

been considered and practiced by refiners for resid conversion is
the ebullated bed technology. In this case, the same deactivation
phenomenon seen in fixed-bed technologies is inherent with
the one exception: the issue of low catalyst cycle length may be
resolved through continuous addition and removal of catalysts.
Every resid handling process is subject to asphaltene precipi-
tation as the saturates and aromatics contained in the feed that
hold the asphaltenes in solution are removed or converted. This
phenomenon is essentially driven by asphaltene-solubility chem-
istry, and the achievable conversion is a function of the saturates,
aromatics, resins and asphaltene content in the residue, which
in effect defines crude compatibility. In most cases, these units
operate at a nominal 55% to 75% conversion, and in an era of
“opportunity crudes”, this inherent limitation must be recognized.
While refinery economics dictate the need to operate at or near
the asphaltene-precipitation boundary limits, the operation of
these units can be fairly complex as the refiner balances the need
to operate at maximum conversion while minimizing reliability
issues associated with asphaltene-induced fouling.
With this narrow operating window, any changes in feed qual-
ity can contribute to higher maintenance costs and low onstream
factors. To achieve a relatively small overall improvement in resid
KPE
Select 164 at www.HydrocarbonProcessing.com/RS
40
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8VLQJ<RNRJDZD¶V3ODQW5HVRXUFH0DQDJHUDQG3676FKHGXOHU
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Select 98 at www.HydrocarbonProcessing.com/RS
 CLEAN FUELS Not Mozart, Yet a
Classical Genius
conversion, and to improve reliability, operators often limit once-
through conversion, recycle polynuclear aromatics (PNAs) and
add other external aromatic-rich streams to help solubilize the
asphaltenes, which, in turn makes the process more capital inten-
sive and will result in higher operating costs. Although these
processes are catalytic and use metal-containing catalysts, the con-
version chemistry is a blend of catalytic cracking and deactivation-
induced thermal cracking. Along with the addition of aromatic
external feeds, the chemistry will result in lower naphtha, diesel
and gasoil qualities requiring the streams to be re-hydroprocessed
to meet Euro V product quality specifications.
This need to add two catalytic steps makes the process capital
intensive, thus challenging the economics of this option. With
declining fuel-oil prices, and tightening fuel-oil quality regula-
tions, the large volume of unconverted fuel oil will leave the
refiner with much of the same issues to deal with in the post
investment scenario, although in a smaller scale. When tested
against the “seven questions to ponder,” the choice of crudes,
achievable conversion, product qualities, reliability and invest-
ment threshold gain significance.

Slurry-phase hydrocrackers. With high crude price and

low natural gas prices on the horizon, slurry-phase hydrocracking
(Fig. 7) is emerging as the preferred approach for upgrading resi-
due streams via hydrogen addition. The principles of slurry-phase
hydrocracking essentially overcome the limitations of fixed-bed
and ebullated-bed technologies and provide for substantially
higher conversion of the residuum.
The primary conversion of residues can be achieved through
either catalytic or noncatalytic routes. Investigations for using
catalysts or noncatalytic additive systems for primary conversion
of the residues can be traced back to the early 1900s and span
the entire century, with several hundred patents that have been
awarded in support of these activities. Over the past few years,
substantial effort has been expended by technology providers
exploring nanocatalysts to enable the primary conversion of resi-
dues at marginally lower operating pressures. While catalyst-based
systems are technically viable, the use of a relatively expensive cata-
lyst system, catalyst deactivation, low quality of derived products Just like Mozart‘s compositions
and the need for catalyst recovery, all contribute to the economic SAMSON‘s Series 240 Valves are
considerations which in the authors’ view, is likely to make this world renowned and appreciated.
option less attractive. Tuned like organ pipes, the Series 240
suits all pressures and flows, from ada-
Key performance criteria. We will focus on the non- gio to allegro. Yet, the valves definitely
catalytic slurry-phase hydrocracking in the context of hydrogen work piano so nobody will be roused
addition and examine the appropriateness of the technology to by a sudden beat of the drum. And, just
the current market conditions. HP like in an orchestra, the number of in-
struments is your choice. With position-
Extended version avaiable online at HydrocarbonProcessing.com. ers, solenoid valves and limit switches,
further virtuoso performers are waiting
Mitra Motaghi is a process engineer with the KBR Technology business unit with to come in.
special focus on resid hydrocracking and VCC technology. She holds an MS degree
in chemical engineering from Texas A&M Kingsville. We supply the instruments,
you be the conductor.
Bianca Ulrich is a principal process engineer with KBR Technology business unit
with special emphasis on resid hydrocracking and VCC technology. She holds a BS
degree in chemical engineering from Georgia Institute of Technology.

Anand Subramanian is Vice President for new technologies with KBR Tech-
SAMSON AG x MESS- UND REGELTECHNIK
nology business unit and is responsible for the VCC technology. He has 24 years
of industry experience and 20 years with KBR in various process and technology Weismüllerstraße 3
management positions. 60314 Frankfurt am Main x Germany
Phone: +49 69 4009-0 x Fax: +49 69 4009-1507 KPE
Select 172 at www.HydrocarbonProcessing.com/RS 䉴 E-mail: [email protected] x www.samson.de
A01007EN

43
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Select 66 at www.HydrocarbonProcessing.com/RS
 CLEAN FUELS SPECIALREPORT

Convert bottom-of-the-barrel
into diesel and light olefins
Integrating residue hydrocracking operations with advanced
fluid catalytic cracking optimizes upgrading of heavy crude oils
M. RAMA RAO, D. SONI, and G. M. SIELI, Lummus Technology, Bloomfield, New Jersey;
D. BHATTACHARYYA, Indian Oil Corp. Ltd., R&D Center, Faridabad, India

G
lobal demand for diesel is pro- ferential between light/sweet and heavy/ ability to upgrade the bottom of the bar-
jected to grow from approxi- sour crudes is driving the market to process rel and to produce high-quality products
mately 23 million barrels per day larger quantities of heavier crudes. There while processing a heavy crude slate are key
(MMbpd) in 2006 to 37 MMbpd by are many options on how to upgrade the drivers for better margins.
2030, while the demand for gasoline is “bottom of the barrel.” Several options have the capability not
expected to increase from 22 MMbpd to Carbon rejection. Among the carbon only for handling heavy crudes using vari-
27 MMbpd over the same period.1 This rejection processes, delayed coking has been ous residue upgrading technologies, but
increase in diesel demand (14 MMbpd) is quite popular recently. Solvent deasphalt- also for tailoring schemes to maximize
almost three times the increase in gasoline ing (SDA) is used to separate residue from high-demand products such as diesel and
demand (5 MMbpd). deasphalted oil (DAO), which is a feed- light olefins. The scheme described here
Gasoline demand in the US and West- stock for fluid catalytic cracking (FCC) or involves the integration of the innova-
ern Europe is expected to stay flat or even hydrocracking units. Although this pro- tive ebullated-bed hydrocracking process
decrease. These trends have led refiners to cess maximizes DAO, the pitch (bottoms and advanced fluidized catalytic cracking
consider various options for maximizing of the SDA unit) contains very high levels (FCC) processes.
diesel production from current operations of Conradson carbon residue (CCR) and The ebullated-bed residue hydrocrack-
and/or adding new units targeted at meet- metal contaminants, thus posing serious ing process is a highly effective hydrogen-
ing this projected new demand for diesel concerns for disposal and/or utilization. addition process that upgrades heavy residue
while improving margins. Visbreaking is also used to reduce residue feeds to good-quality diesel and FCC feed.
Olefin demand trends. Demand for viscosity while maximizing distillate pro- The advanced FCC process is a catalytic
light olefins (ethylene, propylene and duction. Products from all of these pro- cracking process that maximizes light olefins
butylenes)—the building blocks for the cesses require a substantial degree of post from various feedstocks such as vacuum gas-
petrochemical industry—is also growing treatment to improve quality and to meet oils (VGO), atmospheric residues, etc. This
significantly. Several announced steam- desired fuel specifications. scheme is also flexible enough to shift the
cracker projects are expected to produce Hydrogen addition. Conversely, hydro- product slate to meet fluctuations in the
sufficient ethylene to meet new petro- gen addition technologies, such as atmo- marketplace with respect to the required
chemical demand. While the propylene spheric residue desulfurization (ARDS) and products and/or the type of crude processed.
production—a byproduct of liquid-feed vacuum residue desulfurization (VRDS),
steam crackers—will also increase, it will produce better quality products. However, New hydrocracking process. The
be insufficient to meet the growing future because of the high investment and high ebullated-bed residue hydrocracking pro-
demand. In looking ahead, catalytic crack- hydrogen addition requirements, these cessa features high distillate yields while effi-
ing is expected to continue to be the promi- technologies are used for only about 20% ciently removing feed sulfur, CCR content
nent propylene source.2 of the global residue upgrading capacity. and metal contaminants from vacuum resi-
dues. It is safe, reliable and easy to operate.
Adapting to market conditions. New challenges. When determin- Over the years, advances in the ebullated-
The decline in fuel oil demand and tighter ing which process(es) to implement, it is bed residue hydrocracking process have sig-
fuel specifications, coupled with more necessary to broadly examine the refin- nificantly reduced capital investment and
stringent environmental regulations, have er’s many challenges, including possible operating costs while extending the con-
compressed refinery margins. There is a changes in product demand, quality and version and process capabilities, including:
growing drive to cost-effectively maxi- pricing, and the need for the refinery • Hydrogen purification systems
mize production of high-value products to be able to process heavy/sour crudes. • Low treat-gas rates
from every barrel of crude oil processed. Advancements in process technologies play • Integrated hydrotreating/
In addition, the considerable price dif- a crucial role. Now, more than ever, the hydrocracking
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 45
SPECIALREPORT CLEAN FUELS

• Inter-reactor separator/stripper recycle of high-temperature vacuum bot- uid recirculation is increased as a result of
• Third-generation bottoms recycle pan toms to the reactor and the use of aromatic reduced superficial gas velocity and holdup.
• Onstream catalyst addition and diluents, such as FCC slurry oil, help in This also helps in better back-mixing of
withdrawal controlling coke and sediment formation, liquid and catalyst bed, thereby minimizing
• Maintaining constant pressure drop which could otherwise lead to potential incidences of hot spots, catalyst-bed slump-
across the reactor difficulties in maintaining proper catalyst ing, channeling and flow maldistribution.
• Isothermal reactor operation bed ebullation. The advent of membrane The ebullated-bed residue hydrocrack-
• Ability to process heavy, high-metals, purification systems has resulted in very ing process has great inherent flexibility
high-solids content feedstocks. high-purity recycle gas and reduced recy- to meet variations in feed quality and
Integrating the ebullated-bed residue cle gas rates to the ebullated-bed residue throughput, product quality, and reaction
hydrocracking unit with hydroprocessing hydrocracking reactor. This enhances the operating severities (temperature, space
results in significant cost savings. The total reactor operation since internal liq- velocity, conversion, etc).3,4 This is a direct
result of the ebullated catalyst-bed-reactor
system. Online catalyst addition and with-
drawal capabilities facilitate in the control-
ling the catalyst consumption and activity
in response to variations in feed quality
Wouldn’t it be great (metals, sulfur, asphaltenes, etc.) Depend-
if everything was ing on feed quality, diesel and gasoil (FCC
feed) yields in the range of 19 vol%–43
FRACTURE RESISTANT? vol% and 30 vol%–40 vol%, respectively,
can be produced in the ebullated-bed resi-
due hydrocracking unit. Typical operating
parameters, feed quality and product yields
can be found elsewhere.3

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KPE
Select 167 at www.HydrocarbonProcessing.com/RS
46
 CLEAN FUELS SPECIALREPORT

version and selectivity for light olefins. Since • In both cases, refinery crude through- uses a delayed coking unit for residue
all the cracking reactions take place in the put capacity is 200,000 bpsd upgrading as shown in Fig. 1. As indi-
short-contact-time riser reactor, with very • Base refinery is currently processing cated in Table 1, the crude blend consists
high catalyst-to-oil ratio and all high-activ- a blend of 35 vol% heavy and 65 vol% of 35 vol% heavy crude (mix of Maya and
ity catalyst, the selectivity to light olefins light crudes; the reconfigured refinery is Urals) and 65 vol% light crude (Bonny
is very high. The LPG produced contains expected to process 80 vol% heavy crude Light and Sarir).
about 45 wt%–50 wt% propylene. Total • Capacity potential of all existing pro-
olefins in LPG can be as high as 80 wt%. cess units is to be fully utilized Case 1. The refinery upgrade (Fig. 2)
The major concerns when processing • Production of diesel, jet fuel and involves adding a new ebullated-bed resi-
heavier feedstocks having high CCR and propylene is maximized while processing due hydrocracking unit and revamping
metals are: excessive coke make, high regen- the heavy crude slate the existing FCC unit to an advanced
erator temperature, high dry-gas make and • Fuel quality is to meet Euro-IV speci- FCC design. This case is based on the
high catalyst makeup rates. The advanced fications refinery processing 80 vol% heavy crude,
FCC catalyst’s low selectivity to delta coke • Crude and product prices are based as listed in Table 1. The increased volume
and dry gas and its high tolerance to metals, on Rotterdam 2007 average spot prices. of heavy crude results in a higher volume
in conjunction with the advanced hardware Several configurations were investigated of atmospheric tower bottoms (ATB) and
design, allow this unit to easily handle these to meet the objectives of the refinery in a vacuum residues (VR). Part of the VR is
difficult feedstocks. Demonstrating the cost-effective manner. It was found that routed to the ebullated-bed hydrocracking
full flexibility of the advanced FCC pro- incorporating an ebullated-bed residue process to maximize diesel product and to
cess, it can accept feedstocks ranging from hydrocracking unit and revamping the produce feed for the advanced FCC unit.
hydrotreated VGO to heavy residue oils FCC unit to an advanced FCC process The LP modeling studies suggest that a
and can be designed and operated to maxi- would provide significant advantages,
mize propylene, or propylene plus ethylene, especially if a refinery is geared to process TABLE 1. Crude oil slate
or propylene plus gasoline.5 heavy crudes for the cost advantage. This comparison
combination of processes provides the
Process integration/reconfiguration. refinery with greater flexibility to accept Crude Base Case, Case 1,
The refinery considered in this study plans wider variations in crude quality while name bpsd bpsd USD/bbl
to improve its capability to process heavier optimizing refinery margins. For a better Maya 35,000 80,000 60.39
crudes and also maximize diesel, jet fuel understanding of the proposed scheme, Urals 35,000 80,000 64.48
and light-olefin products. The conse- several case studies are presented here. Bonny Light 65,000 20,000 70.57
quences of processing higher quantities of Sarir 65,000 20,000 66.74
heavy crude are: Base Case. The Base Case represents
Total 200,000 200,000
• A substantial reduction in middle the base refinery configuration, which
distillate yields or a higher yield of atmo-
spheric bottoms, leading to limitations in
vacuum tower capacity

Petrochemical
naphtha
• Inferior product quality:
0 Requiring additional treating facili- Lt naphtha HT Lt Nap
ties and/or Hvy naphtha
0 Resulting in secondary processing Crude Crude DC naphtha Naphtha HT Hvy Nap
oil unit Kerosine hydrotreater
units, such as hydrocracking and FCC units, + C5/C6
Sat gas Light GO isomerization
to utilize more hydrogen and/or catalyst. LCGO HT unit
plant
Such a plan is likely to require a sig- Distillate distillates
Atm GO hydrotreater Gasoline
nificant level of capital investment. To pool
optimize the refinery configuration, an HC Lt Nap
in-house linear programming (LP) model Hydro- Reformer
HVGO cracker HC Hvy Nap Reformate
was used that captures the changes in crude Atm
HCGO

residue HC Dist
quality, optimizes product blend to meet
LVGO

LCO
the desired product specifications and esti- LPG
Jet/diesel
HC Bot

mates the incremental utilities required. pool

The model also features economic evalu- FCC
Vacuum FCC gasoline
ation capabilities that account for new unit FCC gasoline
investments, incremental utility costs, cost HVGO + treater
of feed/product, imports/exports, etc. gas
DC C3s plant C4s Alkylate
The LP model initially was configured Alkylation
for a base refinery operation, and then Delayed DC C s SHT
Vac residue coker 4
reconfigured to account for changes in
crude slate and associated effects on the Coke FCC slurry oil
product yields and quality, and changes in
costs. These parameters were used in the LP FIG. 1 Simplified flow diagram of the Base Case refinery.
modeling study:
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 47
SPECIALREPORT CLEAN FUELS

TABLE 2. Comparison of FCC

Lt Nap
feedstock quality

Petrochemical
Base Case Case 1

naphtha
Lt naphtha HT Lt Nap Gravity, °API 22.1 18.7
Hvy naphtha Sulfur, wt% 1.12 2.0
Crude Crude DC naphtha Naphtha HT Hvy Nap Con. carbon content, wt% 1.35 2.5
oil unit Kerosine hydrotreater
+ C5/C6 Nickel, ppmw 0.73 6.2
Sat gas Light GO isomerization
LCGO HT unit Vanadium, ppmw 1.6 13.8
plant Atm GO
Distillate distillates
hydrotreater Gasoline Total nitrogen, ppmw 1,495 2,557
pool
HC Lt Nap
Hydro- Reformer
bed residue hydrocracker bottoms. The
cracker HC Hvy Nap Reformate feed to the advanced FCC unit consists of
Atm
HVGO
LVGO

HC Dist Hvy Nap the heavy vacuum GO (HVGO) cut from

HC Bot

residue
HCGO

LCO the ebullated-bed residue hydrocracking

LPG
Jet/diesel unit and virgin VGO, which is significantly
pool
Vacuum

less than the Base Case feed to the FCC

unit

Diesel FCC unit. To supplement the advanced FCC

VGO FCC gasoline
unit feed, ATB is included as one of the
Advanced FCC

gasoline
+ gas plant

HVGO treater feed constituents. Typically, the inferior

Residue DC C3s C4s Alkylate feed quality of this stream (Table 2) would
hydrocracker/ Alkylation adversely affect the FCC product yield pat-
HT tern and catalyst makeup rate. However,
Delayed DC C4s SHT
Bottoms coker this effect is minimized in the advanced
Vac residue FCC unit as the process can efficiently
Coke
FCC slurry oil handle inferior feedstocks without a cata-
lyst cooler and huge catalyst makeup rates.
FIG. 2 Simplified flow diagram of an upgraded refinery with ebullated-bed residue Despite the inferior feed, propylene and
hydrocracking process and advanced-FCC unit. butylenes production is increased from 5.1
wt% and 4.1 wt% to 17 wt% and 8.2 wt%
TABLE 3. Comparison of process unit capacity in the advanced FCC unit, respectively.
The propylene from the advanced
Case 1
Base Case Incremental FCC unit, after treatment, can be used
Process unit bpsd Ktpy bpsd Ktpy as a petrochemical feedstock. A portion
Crude unit 200,000 9,450 0 340 of the C4s is used to produce alkylate for
Vacuum unit 87,554 4,591 9,430 660
the gasoline pool. Light cycle oil (LCO)
from the advanced FCC unit is processed
Delayed coking unit 29,570 1,701 0 0
in the existing hydrotreater. Distillate from
Ebullated–bed residue — — 20,005 1,173 the ebullated-bed residue hydrocracker is
hydrocracking process
processed in an integrated hydrotreater/
FCC (advanced FCC unit) 27,325 1,401 –3,080 –130 hydrocracker reactor arrangement, with
Hydrocracker 44,810 2,285 6,300 335 the hydrocracker processing incremental
Naphtha hydro treater 27,246 1,159 590 0 virgin VGO. Slurry oil (CLO) is recycled
Reformer 40,651 1,710 –3,160 –160 to the ebullated-bed residue hydrocracker
Hydrogen plant, MMscfd 61 47
as aromatic diluent to minimize coke and
sediments formation. This scheme has the
Amine regeneration, gpm, DEA 1,177 415
flexibility to process a higher quantity of
SRU + TGT, metric tpd 285 — 77 — heavy/opportunity (i.e., lower cost) crudes
C5 isomerization 5,113 195 140 1 and still produce Euro-IV quality fuels and
FCC gasoline HT 15,671 669 –6,680 –290 petrochemical feedstocks.
Alkylation 4,365 171 –115 –4 Table 3 summarizes the feed capacities
C4 SHT unit 4,335 142 –520 –16 of all the processing units. As shown in
Table 3, the revised configuration is able to
Diesel HT unit 67,028 3,180 180 6
effectively utilize the capacities of most of
the existing process units. The FCC gaso-
blend of 80 vol% heavy and 20 vol% light limits on yields and in meeting Euro-IV line hydrotreating unit and C4 selective
crude is optimal because it maximizes the diesel quality. hydrotreating (SHT) unit capacities are
amount of diesel and light olefins. Even The delayed coker capacity is main- under-utilized, as the current objective is
though increasing the heavy crude por- tained equivalent to the Base Case by pro- to reduce gasoline production. As expected,
tion beyond 80% lowers feed cost, it poses cessing a blend of virgin VR and ebullated- hydrogen consumption is increased con-
KPE
48
I FEBRUARY 2011 HydrocarbonProcessing.com
 CLEAN FUELS SPECIALREPORT

siderably and has been considered in the TABLE 4. Product prices and comparison of product rates
evaluation of the refinery upgrade. and imported feeds
Table 4 shows that diesel and jet fuel
product increase from a total of 4,387 Base Case Case 1
Ktpy in the Base Case to 4,556 Ktpy in Products USD/bbl bpsd Ktpy bpsd Ktpy
Case 1. Although it is possible to increase Propylene-PG 74.7 2,401 70 6,316 183
jet fuel production, it was limited to the Euro-IV 92 RON gasoline 76.93 69,511 2,938 63,405 2,664
projected demand of 33% over the Base
Case (i.e., equivalent to 453 Ktpy). Note: Petrochemical naphtha 72.78 33,669 1,319 31,935 1,263
Revamping the existing FCC unit to Euro IV diesel 82.26 87,023 4059 88,370 4,106
an advanced FCC design resulted in an Jet fuel 85.01 7249 328 10,000 453
increase in propylene from 70 Ktpy (Base
Sulfur 25 ($/metric ton) 190 (metric tpd) 67 435 (metric tpd) 152
Case) to 183 Ktpy in Case 1. Even though
the heavy crude content was increased Coke 30 ($/metric ton) 1,303 (metric tpd) 456 1,525 (metric tpd) 534
from 35 vol% (Base Case) to 80 vol% Diesel + Jet fuels 94,272 4,387 98,370 4,556
(Case 1), it was possible to increase the
Imported feeds
quantity of diesel, jet fuels and propylene
by incorporating the ebullated-bed residue Natural gas ($/MMBtu) 7 444 (metric tpd) 155 364 (metric tpd) 127
hydrocracking and advanced FCC units. MTBE 90.07 6,750 281 7,038 294
Otherwise, the middle distillates yield/
quantity would have been much lower TABLE 5. Total installed cost, gross
than that of the Base Case. The incremen- Rama Rao Marri is a principal process technology
revenue and simple payback engineering specialist at Lummus Technology in Hous-
tal butylenes (98 Ktpy) produced from the ton, Texas. He has more than 17 years of experience
advanced FCC unit are used to produce Investments costs, MMUS$ Base Case 1 in the area of FCC process design, development and
alkylate, meeting the internal fuel require- technical services. He was the co-inventor of the Indmax
ISBL — 590.4 FCC process developed by IOC R&D center for convert-
ments and minimizing natural gas imports,
Utilities + offsites — 178.3 ing heavy feeds, including residue to light olefins, i.e.,
which is a specific requirement in this case. propylene and ethylene. He has about 11 patents and
Alternatively, the incremental butylenes Total installed cost, MMUS$ — 768.7 20 publications/papers to his credit. Mr. Marri has a MS
can also be sold separately as a petrochemi- Gross revenue, MMUS$/yr 576.7 780.7 degree in chemical engineering from Indian Institute of
cal feedstock. Technology, Kanpur, India.
Increase in gross revenue,
MMUS$/yr — 204.0
Economic benefits. The estimated Dalip Soni is the director, FCC Technology, at Lum-
total installed cost for Case 1 is presented Simple payback, yr — 3.77 mus Technology in Houston, Texas. He has 30 years of
in Table 5, together with the gross mar- experience in process design, research, development
and evaluation of petroleum refining and synthetic
gin for the Base Case and Case 1 and the of the barrel, respectively. However, add- fuel processes. The majority of his experience has been
simple payback for Case 1. The economics ing a new ebullated-bed hydrocracker and related to FCC technology having worked on several
of the project are attractive, with an esti- revamping the FCC unit to an advanced design and development projects. He has BS degree in
mated simple payback period of less than design can result in: chemical engineering from Panjab University, India, and
an MS degree in chemical engineering from Oklahoma
3.8 years. The proposed scheme results in • Increased diesel and light-olefins State University.
significant incentives for refiners aiming product yields and quality
at improving crude blend flexibility with • Process integration via feed/product
increased diesel and propylene production. stream sharing Gary Michael Sieli is the director of process plan-
ning for Lummus Technology’s Process Planning Group
Conclusions: Several recent factors • Improved feed quality for FCC unit in Bloomfield, New Jersey, and has been with Lummus
have influenced the refinery outlook: • Ability to handle heavier crudes effi- since 2002. He has a BS degree in chemical engineer-
• Demand and growth of diesel com- ciently and more cost effectively. ing from the New Jersey Institute of Technology and
pared with gasoline, coupled with stringent These advantages make the combination an MS degree in chemical engineering from Rutgers
University. Mr. Siele has authored several papers on
automotive fuel specifications of the ebullated-bed residue hydrocracking refinery planning, heavy oil upgrades and delayed cok-
• The use of the refinery as an alternate process and the advanced FCC units an ing, and has more than 32 years of experience in the
source for petrochemical feedstocks, lead- attractive option for refiners. HP refining industry.
ing to integration of refinery operations
with a petrochemical complex LITERATURE CITED
Debasis Bhattacharyya is a senior research
• Shrinking refinery margins due to For complete literature cited, visit HydrocarbonProcessing.com.
manger in the R&D Center of Indian Oil Corp. Ltd. He
higher/volatile crude oil prices, which holds a B. Tech degree in chemical engineering from
NOTES Calcutta University and M. Tech degree from Indian
increase the need to process opportunity/ a The process is licensed by Chevron Lummus Institute of Technology, Kanpur. He joined Indian Oil
inferior feedstocks into useful products Global (CLG), a joint venture between Chevron in 1991 and has been engaged in providing technical
while enhancing yields, product quality U.S.A. Inc., a wholly owned subsidiary of services to refineries on catalyst selection, process opti-
and selectivity. Chevron Corp., and Lummus Technology, a mization, troubleshooting, revamping various refining
To address these issues, many existing CB&I company. processes and also the development and commercializa-
b Process developed by Indian Oil Corp. Ltd.’s tion of new technologies. He holds 10 US patents and
refinery configurations include an FCC Research & Development center, with the state- authored more than 35 papers in national and inter-
unit and delayed coker to maximize gaso- of-the-art FCC/RFCC technology and know-how national journals and symposiums. He is a member of
line production and to upgrade the bottom of Lummus Technology. Indian Institute of Chemical Engineers.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 49
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 CLEAN FUELS SPECIALREPORT

What are the future fungible

transportation fuels?
Alternatives hold promises to decrease dependence on crude oil,
but they also uncover other challenges in distribution and engine use
M. STOCKLE, Foster Wheeler, Reading, Berkshire, UK

T
he drive to reduce carbon emissions Current transport fuels. If we are to tion. The advantages and disadvantages of
has resulted in the development of consider the fungibility of alternative fuels, each fuel are discussed here:
a number of alternatives to diesel we first need to understand the specifica- Ethanol. The amount of ethanol that
and gasoline for transport fuels. One of tions for present-day transport fuels. The can be blended into the gasoline pool is
the key factors influencing how readily major transport fuels used are gasoline, die- generally limited to 10% (although the
these fuels could be adopted is the level sel, jet kerosine and marine bunker fuel. The US has just gone to E15 (15% blend) for
of infrastructure investment required and main focus of government legislation has 2007+ cars and light trucks). This limita-
how readily these fuels can make use of been on fuels used in the road transport tion is imposed by current car engines and
the existing distribution systems. Based industry, that is, gasoline and diesel. These
upon recent studies, there are a number two transportation fuels will be the focus of TABLE 1. Gasoline specifications
of these alternative fuels, and this article this discussion. from the Worldwide Fuels Charter
will summarize the advantages and chal- Category 4
lenges of each alternative, paying particu- Specifications. The fuel specifications
lar attention to how readily these fuels can for both gasoline and diesel are generally Property Value
be used within the existing infrastructure set by either state or national government
RON 95
and fleet. with significant variation around the globe
between the specifications required. How- Rvp, kpa (varies by region) 65
Drive for alternative fuels. The ever, the drive towards clean (low-sulfur) Aromatics, vol% max 35
use of transport fuels other than mineral fuels and pressure from engine manufactur-
Density, kg/m3 715–770
oil-derived gasoline and diesel is driven ers to have consistent specifications globally
by two main concerns—climate change have seen a general convergence in current Benzene, vol% max 1
and security of supply. These drivers have or planned fuel specifications world-wide. Oxygen content, wt% 2.7 max
seen a number of governments introduce Key differences now generally relate to the
Olefins, vol% max 10 max
targets regarding renewable content of the progress toward clean fuel mandates by the
transport fuel pool. Often, these targets individual countries. Sulfur content, wt ppm 10 max
are influenced not only by the sustainable The key global specifications are those Ethanol, vol% 10 max
level of production for the renewable fuel used in the US and the European Union
but also how fungible the renewable is in (EU). To illustrate the typical qualities of TABLE 2. Diesel specifications
comparison to existing fuels. gasoline and diesel, this article will use
from the Worldwide Fuels Charter
Fungibility is defined as “the property specifications from the Worldwide Fuels
of a good or a commodity whose indi- Charter Category 4 (as this reflect the Category 4
vidual units are capable of mutual sub- general trend in fuels specification) to Property Value
stitution.” For a transport fuel to be fully reflect these key performance and qual-
Cetane index 51
fungible, it must be capable of completely ity targets. Table 1 summarizes the key
replacing the current mineral oil-derived specifications from the Worldwide Fuels Density, kg/m3 820–840
fuel in the present infrastructure. Given Charter Category 4 for gasoline; Table 2 Sulfur content, wt ppm 10
this definition, this article only considers lists diesel specifications.
T95 boiling point ASTM D86°C 350
gasoline and diesel replacements and not The alternative fuels considered here can
fuels like hydrogen or electricity, which be split into either gasoline or diesel replace- FAME content, vol% 5
would be consumed in completely differ- ments. Table 3 lists fuels to be considered. CFPP, °C –5
ent engines/power trains and for which Gasoline replacements. Table 4 com- Viscosity @ 40°C cst 2–4
the distribution infrastructure is com- pares the typical properties of gasoline
pletely different. replacements with the gasoline specifica- Flash Point, °C 55
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 51
 KPE
Select 54 at www.HydrocarbonProcessing.com/RS
 CLEAN FUELS SPECIALREPORT

by the present infrastructure. This is due rather than on a two-chain carbon mol- as a gasoline-blendstock without further
to the corrosive nature of ethanol—some ecule. However, butanol has some advan- processing, due to the very low octane of
engine components and parts of the infra- tages and some disadvantages when com- the product.
structure (for example, filling nozzles on pared to ethanol. However, FT naphtha can be further
pumps)—need to be specifically designed On the plus side, because butanol has processed to improve the octane, with
to handle higher ethanol concentrations. a higher molecular weight than ethanol, it light naphtha routed to an isomerization
Blending ethanol into the pool also has lower vapor pressure, lower water solu- unit and the heavy naphtha reformed to
produces challenges in meeting gasoline bility and a higher energy density. The first improve octane. The isomerate and refor-
specifications. Ethanol appears to be a good two attributes mean that it can be more mate produced are identical in their prop-
blendstock, but if we look at the measured easily added to gasoline than ethanol. In erties to those produced from similar units
properties of pure ethanol, when added to addition, it is less corrosive than ethanol; processing fossil-derived naphtha. How-
the gasoline pool, it behaves in a far from thus, it can be more easily transported in ever, this does not mean that an on-speci-
ideal way. The key impact is that ethanol pipelines and used in vehicle engines in fication gasoline can be produced from FT
raises the Rvp, so that the Rvp of the blend higher blend concentrations than ethanol
is higher than either of the blend compo- without the need for extensive modifica-
nents. This can make it difficult to add tions. The lower oxygen content of butanol ■ We could potentially
ethanol to gasoline pools that are already means that more can be blended into the
tightly constrained on Rvp. pool before the oxygenate specification is combine technologies to
Ethanol also presents problems when reached. In theory, butanol can be blended
transporting fuels. The key issue is that at about 18% rather than the 10% limit
produce fully fungible
ethanol is soluble in water. If a gasoline for ethanol. On the down side, butanol is gasoline and diesel
blend with ethanol comes into contact more toxic than ethanol. Unlike ethanol,
with water, the ethanol will preferentially there is no body of experience in its appli-
TABLE 3. Fuels considered
dissolve in the water, not only contaminat- cation as a transportation fuel.
ing the water but also possibly sending the Fischer-Tropsch naphtha. The con- Gasoline Diesel
gasoline off-specification. This means that version of biomass into syngas and then replacements replacements
ethanol needs to be added into the blend into hydrocarbons via the Fischer-Tropsch
Ethanol Fatty acid methyl esters
as late as possible, generally at the termi- (FT) process is a prime candidate for pro-
(FAMEs)
nal before distribution to retail outlets, but ducing alternative transport fuels. While
after transportation by pipeline or ship. this process is primarily aimed at produc- Butanol Hydrotreated vegetable oil
Therefore, refiners often have to blend ing diesel, it also produces some naph- Fischer-Tropsch (FT) Fischer-Tropsch diesel
some or all of their gasoline in such a way tha. This naphtha is primarily paraffins naphtha
that ethanol is not in the pool but that the with traces of aromatics; thus FT naph-
Di-methyl ether (DME)
pool is blended to meet the specifications tha cannot be used as gasoline or even
after the ethanol is added. A number of
vehicles are now being produced that can TABLE 4. Properties of gasoline replacements
run on 85% ethanol (E85) blends and this
offers the opportunity for more extensive Property Gasoline spec Mineral gasoline Ethanol Butanol FT naphtha
use of ethanol. However it would require RON 95 95 1071 96 10
a separate distribution system and sepa- Density, kg/m3 715–770 740 794 814 700
rate pumps at retail stations to avoid issues
with contamination. Benzene, vol% 1% max 1% 0% 0% 0%
Despite the challenges of using etha- Aromatics, vol% 35% max 35% 0% 0% 2%
nol, it is still the most widely used alterna- Oxygen, wt% 2.7% max 2.7 34.8% 21.6% 0
tive to gasoline, and Brazil has been run-
Rvp, Mpa 65 kpa 65 2 6.43 40
ning higher ethanol blends (20%–25%
ethanol) for some time. In Brazil, it is Sulfur, wt ppm 10 ppm 5 ppm 0 0 0
easy to produce ethanol from a number 1 A higher figure is often used for blending due to interactions in the pool.
of readily available feedstocks; it is also 2 Ethanol interactions with gasoline are nonlinear and effective Rvp of ethanol is different to the pure Rvp and varies depending
possible to use more sustainable, non-food 3
on the level of ethanol blended into the pool. The figures used are generally higher than the specification for the blend.
Figure used for blending.
competing feedstocks in the future. The
infrastructure issues can be overcome as TABLE 5. Properties of diesel replacements
was demonstrated in Brazil by having flex-
fuel engines and upgrading pumps. But Property Diesel Spec Mineral Diesel FAME HVO FT Diesel ME
there is a cost associated with this. Over-
Cetane 51 51 50–65 70–90 70–90 55
all, ethanol can be considered only partly
fungible, as market penetration beyond Density, kg/m3 820–840 840 880 770–800 770–800 Gaseous at normal
10% of the pool would require dedicated conditions
infrastructure. FAME, vol% 5% max 0% 100% 0% 0% 0%
Butanol. This alcohol (butanol) is simi-
lar to ethanol but is based on a four-chain CFPP, °C -5 -5 -5–13 -30– -5 -30– -5 N/A
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 53
SPECIALREPORT CLEAN FUELS

naphtha as it is almost impossible to blend compared to diesel specifications from the Hydrotreated vegetable oil and FT
gasoline from just isomerate and reformate Worldwide Fuels Charter Category 4. diesel. Although hydrotreated vegetable
if a Euro V type specification is to be met. FAME. Fatty acid methyl esters oil (HVO) and FT diesel are produced
This is due to the octane (aromatics) Rvp (FAME) are produced from triglycerides by different processes, the products from
limitations of the blend. In this case, every found in animal and vegetable oils. The the two processes are very similar. The
time the blend is changed to meet one of triglycerides are reacted with methanol materials can be considered as being the
the specifications, one of the other specifi- (or ethanol to make fatty acid ethyl esters same for the purposes of evaluating their
cations is exceeded. (FAEE) to produce three esters and a fungibility. HVO is produced from direct
To produce an on-specification blend- glycerine. FAME has some pluses and hydrotreating of vegetable oil, producing
stock, a third component is needed, such as minuses as a diesel blendstock. It has three long-chain hydrocarbons and a pro-
ethyl tertiary-butyl ether (ETBE) or alkyl- good cetane, but its high density makes pane molecule from each triglyceride fed
ate. Ethanol is not that useful due to its it hard to blend into some pools. The big- to the process. The properties of the pro-
impacts on the already constrained Rvp gest drawback is that FAME is corrosive duced diesel are dependent on the process
of the pool. This means that although FT and can only be blended at relatively low used with a better quality diesel produced
naphtha is highly fungible, once processed, levels into diesel. It can also “go off speci- from a dedicated process where the prod-
it is not fully fungible; a fully on-specifica- fication,” and, so, it can only be stored uct can be isomerized from a straight-chain
tion product cannot be produced from FT for a relatively short time. The level of to a branched-chain structure.
naphtha on its own. FAME is limited to 5% by European FT diesel produced from biomass
(Euro V) diesel specifications. This may via syngas is very similar to HVO once
Diesel replacements. Table 5 shows be relaxed to 7%, but is unlikely to move the FT wax has been hydrocracked and
the properties for diesel replacements beyond this. isomerized. The products consist almost
entirely of paraffins and, in many ways,
make an excellent diesel. It is certainly
a very good blendstock for mineral oil-
100
derived diesels. There are some challenges.
90
80 Cold-flow properties can be a problem,
70 although this can be improved somewhat
60 by isomerization.
50 The density of the diesel from FT and
40 HVO can also be a problem; typically they
30 are in the range 770 kg/m3 to 800 kg/m3.
20 Thus, they are well below the minimum
10 specification of 820 kg/m 3. This is not
0
Mineral Ethanol Butanol FT naphtha Mineral FAME HVO/ DME a major problem for engines, but could
gasoline (processed) diesel FT diesel produce issues with consumers achieving
much lower mileage because of the lower
FIG. 1 Fungibility of alternative fuels as a percentage of total blend. energy density.
A bigger challenge is that the almost
total lack of aromatics in HVO and FT die-
sel can cause problems in engines that have
been run previously on mineral-derived die-
Ferment ETBE Gasoline sel. The aromatics in the mineral-derived
diesel replace the plasticizers in rubber
Alkylation and plastic. When pure FT diesel is run,
the aromatics are stripped out leading to
embrittlement and failure of seals and hoses
C4 in the engine. It may be theoretically pos-
Dehydrogenation
isomerization
sible to overcome this problem by produc-
Biomass ing kerosine-range aromatics material from
Isomerization alkylation of gasoline-range aromatics and
olefinic liquefied petroleum gas (LPG) to
LPG improve not only the aromatics content but
CCR Fractionation
also the density of the blend. The aromatics
problem can also be overcome by limiting
Alkylation the amount of FT diesel in the blend to
around 50%, meaning that FT diesel, while
Gasification FT HCK Diesel highly fungible, is not fully fungible.
Dimethyl ether. Another molecule
being evaluated as a diesel replacement is
FIG. 2 Possible links for clean fuels and blending components. dimethyl ether (DME). This ether can be
run in conventional diesel engines with
KPE
54
I FEBRUARY 2011 HydrocarbonProcessing.com
 CLEAN FUELS SPECIALREPORT

some modifications. It is produced from produce fully fungible fuels, the develop-
methanol made from syngas. DME behaves ment of some new and existing technolo- Mike Stockle is chief engi-
neer—Refining Technology and
more like LPG than other conventional gies means that we may not be far away currently works in Foster Wheeler’s
fuels, and this means it needs a separate from a direct replacement for fossil-fuel- Business Solutions Group in Read-
handling and distribution system similar to derived-transport fuels. The facilities to ing, UK. He graduated from Notting-
LPG. DME is not really compatible with produce these fully fungible fuels will be ham University in 1995 and is a Chartered Engineer
and a Fellow of the IChemE. During his time at Foster
conventional diesel. Given this, DME is more complex and will require a level of Wheeler, he has worked on a number of refining
not considered fungible. integration between facilities. Getting this projects ranging from a grassroots refinery config-
Moving forward. Fig. 1 summarizes integration right will be key to the attrac- uration studies and FEEDs, through major refinery
the limits on the blending of each of the tiveness of the process, and this will involve revamps. Mr. Stockle is an experienced LP modeller
and has undertaken a number of studies looking at
alternative fuels considered. We can see a holistic approach assessing a wide range the impacts of changing markets and legislation on
from the figure that none of the alterna- of possible options. HP refineries across the globe.
tive fuels commonly considered is actually
100% fungible. None can be used directly
as a fully on-specification substitute for
either gasoline or diesel. This does not
mean that there are no replacements for
gasoline and diesel. But these replacements
may need to meet different specifications
and possibly also require different distribu-
tion systems. For example, an E85 gasoline
could be produced from ethanol and FT
naphtha, but this would require different
distribution systems.
It may also be possible to produce
fully fungible fuels by further processing
some of the alternative fuels considered.
This article has already considered the
option of reforming and isomerizing FT
naphtha. Combining this product with
butanol may produce an on-specifica-
tion gasoline and further processing of
the LPG from the FT process or from
hydrotreating butanol should allow pro-
duction of a third blendstock for gasoline,
and thus meet the current specifications.
Combining dehydration with alkylation,
oligomerization or ether production
(ETBE) should provide a blendstock that
allows a non-fossil-fuel-derived gasoline
to be produced.
Diesel may be more challenging;
but, even here, there are options. Pro-
ducing pyrolysis oil from biomass and
hydrotreating this material could produce
aromatics containing a high-density mate-
rial that, when blended with FT diesel,
will produce a fully on-specification mate-
rial. It may also be possible to boost the
aromatics content and density by combin-
ing gasoline-range aromatics with olefinic
LPG to produce an aromatic kerosine-
range material.
Fig. 2 shows how we could potentially
combine technologies to produce fully
fungible gasoline and diesel. We have seen
that there are a number of challenges in
moving away from fossil fuels while mak-
ing as much use of the existing infrastruc-
ture as possible. We have also seen that,
while current proven technologies cannot
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 CLEAN FUELS SPECIALREPORT

How to fabricate reactors

for severe service
Many critical factors are involved in the design
and welding of hydrocracking reactors
D. QUINTILIANI, G. FOSSATARO and M. DE COLELLIS, Walter Tosto SpA, Chieti, Italy

D
emand for transportation fuels and other crude oil-based • Arab hydrocracking of VGO with 70% conversion mode
products has been increasing. To meet growing demand single-stage once through ( SOT)—1,800 psia–2,000 psia (12.4
for “cleaner fuels,” refiners are using more severe processing Mpa to 13.8 Mpa)
methods such as hydrocracking. Demand for refined products has • Arab hydrocracking of VGO with 100% conversion mode
increased to the extent that refiners desire larger hydrocracking reac- TSREC—1,800 psia–2,000 (12.4 Mpa to 13.8 Mpa).
tors that can operate at higher pressures with design conditions that Typical variability of starting operation temperature of the
are even more severe. New feedstock diets for refineries utilize more catalyst in various treatment schedules are:
difficult to “crack” crudes; demand for reactors that can withstand • SSOT, 390°C to 430°C
higher temperatures (over 450°C) and higher hydrogen partial pres- • Second phase of optimized partial conversion (OPC) or
sures (12 MPa to 15 MPa) likewise is increasing. Under such severe TSREC, noble metal catalyst/zeolite, 290°C–350°C, catalyst and
processing conditions, reactor vessels are constructed from low alloy base metal/zeolite, 320°C–400°C.
chromium (Cr)-molybdenum (Mo) steel of various grades. As shown here, the severe operating conditions—high tempera-
ture, high pressure and high partial pressure of hydrogen—increase
Severe processing environment. Hydrocracking or crack- the activity of the catalysts. And only under these harsh conditions
ing, in the presence of hydrogen or dehydrogenating, is a cata- can the best performance be expected from catalyst materials; and
lytic process; heavy oils are converted into lighter fractions. The therefore, the refining operations can be more effective.
upgrading is done by several chemical reactions and involves the
saturation of aromatics, cracking (breaking the bonds of chains Designing for severe service. Under these extreme con-
of Carbon NDR) and isomerization in the presence of hydrogen. ditions, reactors need to be constructed from high-performance
Hydrocracking is, therefore, one of the two major conversion materials that are both resistant to high pressure at high tem-
processes used by the modern refining industry. The other impor- perature and are resilient to corrosive attack from the inside. In
tant process is the fluid catalytic cracking (FCC). However, this fact, the majority of hydrocracking reactors in operation today,
processing operation is mainly used to produce gasoline. are built from a low alloy Cr-Mo type 2.25Cr-1Mo steel. But
“Cracking” operations play a more versatile role in refining the trend in recent years is to build hydrocracking reactors with
hydrocarbons. This process can be adapted to produce middle materials with even better performance. A new generation of
distillates; thus, it is widely adopted due to its ability to pro- steels such as low alloy Cr-Mo with enhanced vanadium (V)
vide a wider range and higher yield of quality products. Typical 2.25Cr-1Mo-0.25V [plate steel SA542 D4a and forgings SA336
products from hydrocracking include: liquefied petroleum gas F22V (P-No.5C-ASME IX)].
(LPG), naphtha, jet fuel (kerosine), diesel, ethylene, lubricating Usage of better-performance materials has increased the service
oils and gasoline. life of high-pressure vessels and can exceed the service life length as
compared to those manufactured with more conventional materi-
Process level. The chemical reactions of the hydrocracking als, even in cases where hydrogen partial pressures are higher than
processes are grouped into two broad classes. The first group those comparable to conventional 2.25Cr-1Mo reactors.
includes hydrotreating reaction, during which impurities—such The industry has seen that 2.25Cr-1Mo-0.25V can provide
as nitrogen, sulfur, oxygen and metals—are removed from the better mechanical properties at room temperature, hot and
hydrocarbon mixture. The second group of reactions involves creep as compared to conventional 2.25Cr-1Mo. In short, the
hydrocracking, in which the carbon-carbon bonds are broken 2.25Cr-1Mo-0.25V, when compared to conventional 2.25Cr-
with the help of hydrogen, using bifunctional catalysts. Typical 1Mo, is considered to be:
variability of hydrogen partial pressure in representative appli- • Stronger in tensile strength at elevated temperatures
cations is: • Less vulnerable to temper embrittlement
• Mild hydrocracking of vacuum gasoil (VGO), Arab or Urals: • Less vulnerable to hydrogen embrittlement
800 psia to 1,200 psia (5.5 Mpa to 8.2 Mpa)—depending on the • Less vulnerable to hydrogen attack
desired operating period • More resistant to weld overlay disbonding.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
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ADVANCED FIRED HEATER TRAINING

Dial up your knowledge

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 CLEAN FUELS SPECIALREPORT

The American Society of Mechanical Engineers (ASME) in lighter weight reactor. The industry cannot deny these benefits as
the Boiler and Pressure Vessel code has also recognized these they give considerable economic advantage.
advantages. In the ASME VIII Division 2 Ed. 2007, these addi- Manufacturers are becoming more confident in the construction
tions are listed: of V-steel vessels and are able to assist the engineering, procurement
• Design stress intensity changed for this material, ASME and construction (EPC) companies in the evaluation of possible
Code Allowable Stress Intensity Changed alternatives, even hybrid solutions between plate and forgings to
• 2007 ASME Section VIII Division 2 Pressure Vessel assess the best results in terms of operational safety, quality and cost.
Code permits significantly higher design-stress intensities for Another aspect to consider is the inside surface protection.
2.25Cr-1Mo-0.25V steel than the previous edition: Classically, hydrocracking reactors need to protect their inner
2004 Edition: 169.1 MPa @ 454°C, 163.0 MPa @ 482°C surface from direct contact from process fluids. This protection is
2007 Edition: 199.8 MPa @ 454°C, 164.6 MPa @ 482°C. provided by an internal liner that is capable of protecting the base
The conventional 2.25Cr-1Mo material properties are: metal from high-temperature corrosion. This cladding is typi-
• 2004 Edition 127.8 MPa @ 454°C, 110.0 MPa @ 482°C cally carried out by overlaying a weld metal over the base metal.
• 2007 Edition 149.8 MPa @ 454°C, 112.0 MPa @ 482°C.
The significant revision of the allowable stress intensity from the
2004 Edition to the 2007 Edition of the Code, shows, at 454°C
an increase of 18.2%, and, in the 2007 Edition, shows an overall
increase of the V-modified steel over conventional material of
33.3%. This increase above conventional material means that the
V-modified steel will have even greater application in the future.

Cost issues. Thanks to all these benefits, reactors can be built

lighter and, therefore, cheaper. For the reactor manufacturer, this
translates into fewer and lighter movements in the factory, easier
transportation, lighter loads on the roads and lighter lifting, which
opens up crane availability and using a lighter crane while loading
on a ship or during erection, which means less cost. The founda-
tions where the reactor will sit can now afford to be lighter and FIG. 1 Macro of 2¼Cro-1Mo-¼V decarburization and fissuring in
high-temperature hydrogen service.
shallower. Each of these activities provides cost benefits with a

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HYDROCARBON PROCESSING FEBRUARY 2011
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SPECIALREPORT CLEAN FUELS

This process of weld overlay uses austenitic stainless steel, usually these projects to reliable manufacturers—experts with credentials.
the type SS 347, niobium-stabilized to resist the phenomenon Some of the risks in using 2.25Cr-1Mo-0.25V are:
of precipitation of carbides at the grain boundary, in particular, • Greater sensitivity to weld cracking during fabrication
during construction and, especially, during post-weld heat treat- • Susceptible to re-heat cracking
ment (PWHT). • Intermediate stress relief (ISR) mandatory for highly
However, the real purpose of the cladding is for process service stressed-pressure retaining welds and catalyst-bed supports zone
of the reactor—namely preventing hydrogen (H2) and other cor- • Greater control required on preheat and inter-pass tem-
rosive media attacks on the base metal wall of the reactor. A major peratures
problem is that an H2 attack can provoke: • Higher weld-metal hardness compared to the conventional
• Decarburization of the surface as carbon migrates to the 2¼ Cr-1Mo steel
surface of the material exposed to the process fluids • Difficult to guarantee toughness for the V-modified steel
• Carbon at the surface combines with the free hydrogen to with 54 joule impact energy level at –29°C.
form methane (CH4) and causes blistering on the undersurface • Welding consumables suppliers are limited globally
(see Fig. 1). • Very low toughness of “as welded” weld deposit prior to
PWHT, can cause:
Tough fabrication process. Following so many positive o Cracking from not carrying out ISR for sufficient time
characteristics, there must be another side to this coin. And there for nozzle welds
is, in fact, the only weak link in this design-materials-construc- o Cracking resulting from weld flaw in nozzle welds
tion-in service chain is limited to fabrication. All the potential o Cracking resulting from cutting nozzle opening through
risks are borne by the manufacturer, so it is necessary to assign a bed support weld build up after DHT

TABLE 1. Procedures for weld types in reactor construction

Before PWHT After PWHT After hydro test
Longitudinal welding MT–TOFD–MANUAL U.T. MT–TOFD–MANUAL U.T. MT–TOFD–MANUAL U.T.
Circumferential welding MT–TOFD–MANUAL U.T. MT–TOFD–MANUAL U.T. MT–TOFD–MANUAL U.T.
Nozzle welding MT – MANUAL U.T. PHASED ARRAY MT–MANUAL U.T. PHASED ARRAY MT–MANUAL U.T. PHASED ARRAY
Overlay PT–UT–FERRITE PT–UT

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I FEBRUARY 2011 HydrocarbonProcessing.com
 CLEAN FUELS SPECIALREPORT

• Field-weld repairs are much more difficult to carry out, due In addition to these two parameters, the temperature profile is
to heating steps necessary in the welding process. critical. It is essential that the temperature is the same all the way
through the reactor body, and that during the temperature rise
Critical quality issues. Material quality from the mill is and fall, the differences in metal temperature is minimal.
critical; consumable-material quality and management are also Problems for reactors where temperatures of the PWHT are
critical. V-modified steel is difficult to work with and it needs not homogeneous can include:
to be managed well. The manufacturer needs to properly plan • Potentially leave residual welding stresses and generate new
the construction of the reactor or vessel. From initial material stresses due to the different temperatures in various parts of the
handling, through to cutting, rolling, beveling, welding, heat reactor
treating and non-destructive testing (NDT) inspection, all need • Reduce toughness (and risk H2 attack) in the zones under
to be tackled by skilled trained personnel. temperature
Moisture problems. The real price to pay for its advantages in • Increase hardness in the zones under temperature
mechanical properties is that V-modified steel is extremely difficult • PWHT at over temperature with over soak (e.g., 720°C/12
to weld. To make the welding easier, an increased overall material h) along with higher X factor and J factor, can compromise step-
management system of the welding process and welding consum- cooling test results (an accelerated thermal aging test)
ables are necessary. In particular, electrodes and flux are subject
to intense drying, between 350°C and 400°C, and maintained at 13.0
temperatures well above 130°C, to remove any sign of moisture. 12.5
Moisture is extremely harmful inside the welding process; mois- 12.0
11.5

Pressure, Mpa
ture contains hydrogen—the primary element for cracking. It is
11.0
imperative that even the welding material held in the welding
10.5
equipment during the feeding process of the weld should be kept at 10.0
elevated temperatures. The elevated temperatures help avoid form- 9.5
ing condensation and ensure that when weld consumable material 9.0
reaches the weld zone, it is dry and fully cleared of moisture. 8.5
8.0
Managing the welding and controlling the heat treatments 20 25 30 35 40 45 50 55
helps to obtain the desired mechanical properties, especially Temperature, °C
the required toughness. From historical evidence, typically the FIG. 2 Minimum pressure temperature cure.
heat-affected zone is the weakest area in most welded metals. In
V-modified steel, regarding toughness at low temperatures, the
critical zone is the area melted—the weld deposit. Today, despite
all the technological efforts, the filler material still faces some dif-
ficulties keeping up with the requirements of industry.
The welding consumable materials are characterized by very
low storage of hydrogen, specifically designed for welding steels
with 2.25% Mo, 1% Cr, 0.25% V, resistant to creep and hydrogen
attack. The weld metal is resistant to embrittlement caused by the
high-temperature service, and is verified during step cooling tests.
The values—“X factor” and “J factor”—are very low, on average
below 15 and 100, respectively.
Another important factor in fabricating reactors in
2.25Cr-1Mo-0.25V is the PWHT. In fact, compared to the con-
ventional 2.25Cr-1Mo, V-modified steel requires a higher tem-
perature PWHT with longer holding times, typically 710° +/–5°C
for 8–9 hours.
Critical temperature parameters. Specialists in this field
recognize that the weld metal on these types of materials has a
critical PWHT temperature of 705°C and a holding time at that
temperature for at least 8 hours. These two parameters of tem-
perature and holding time are higher than the standard required
by ASME where:
• ASME VIII Div. 2 Ed. 2009b Table 6.11 for P-No.5C states
a minimum 675°C
• ASME VIII Div. 2 Ed. 2009b Table 6.11 P-No.5C states a
Holding time minimum for tn < 50 mm 1h
• Many specialists consider these temperatures and holding
times to be insufficient.
Therefore, to have good mechanical properties of materials in
welding, PWHT is carried out at higher temperatures and over
longer periods of time in special furnaces capable of treating whole FIG. 3 Circumferential welding of 2 x 2¼Cro-1Mo-¼V shell cans
or sections of reactors from 800 tons to 900 tons. with preheat burners.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
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SPECIALREPORT CLEAN FUELS

1Mo-¼ V alloy for service with hydrogen at high pressures and

temperatures is under continuous review. American Petroleum
Institute’s publication of API 934-F is under development exclu-
sively for this topic.

Reactor fabrication. In summary, there are only a small

number of key factors that greatly influence safer reactor fabrica-
tion. Intensive training of all personnel involved in the fabrica-
tion and inspection of the reactor is paramount. It is important
that each individual takes responsibility and care for himself, his
(her) fellow workers, as well as the entire team. The importance
of special care required in the management of welding consum-
ables is also illustrated here. We have highlighted the importance
of good reliable automated process control during each of the
welding phases—from pre-heating, to welding, to post-weld
heat treating. Control of the complete manufacturing process
should be guaranteed by developing and following specific weld-
FIG. 4 Submerged arc welding (SAW) of the 2¼Cro-1Mo-¼V shell
cans. ing procedures, and by fixing welding parameters in production
with automatic continuous recording and control methods. To
minimize the risk of premature brittle fracture, it is advisable to
• PWHT and other cumulative heat treatments influence the have an ISR furnace in the shop. It is indispensable to be critical in
properties of materials (base metal and weld metal). NDT, as small indications can propagate into larger failures. Con-
It is clear that the target must be to create a homogeneous sequently, specific training and qualification are required for all
temperature profile over the whole reactor, where the temperature technicians and operators. Finally, and arguably most importantly,
gradient must be steady enough to ensure that temperature dif- it is important to have reliable execution of PWHT procedures,
ferentials do not occur through the thickness of the metal. Also, with well controlled furnaces and skilled personnel to guarantee
it can be demonstrated that the PWHT during construction plays precise temperature curves with a temperature profile no greater
a vital role in determining the service life of the reactor, and that, than +/- 5°C. HP
critically, any one activity can jeopardize the success of a project,
but none more so than PWHT. A well-executed PWHT can be BIBLIOGRAPHY
proven to extend the service life of the reactor. ASME CODES
API 579
API 934-A & -B
Non-destructive testing. Another very important aspect in API 941
the construction of the reactors is nondestructive testing (NDT).
For reactors in 2.25Cr-1Mo-0.25V, the acceptance criteria are
necessarily higher and more stringent than conventional steels.
Even small indications may give rise to problems later in fabrica-
Davide Quintiliani is an international welding technologist
tion, where they can be a trigger for defects with greater impor- and international welding inspector, and II Level of several NDE
tance, such as cracks. Table 1 lists examples of typical examination techniques. He joined Walter Tosto in 1996 as a quality control
procedures used on certain weld types in the manufacturing cycle. Inspector; in 2004, he became head of the quality control depart-
ment with roles of NDE and welding coordinator. From 2008 to
present, he is the head of the welding department, chief welding coordinator and
Fitness for service. A final consideration should be made to material selection specialist. Mr. Davide has a degree from the University of Chieti
the minimum pressurization temperature (MPT). Process equip- G. D’Annunzio, in health and safety at work and a second degree in techniques of
ment fitness-for-service assessments using API RP 579 is a sophis- loss prevention at work and the environment. He has authored 24 technical articles
ticated prediction tool to assess the metallurgical condition of a regarding PED, quality, NDE and welding.
section of process equipment. The analyses of stresses and strains
of pressure equipment can assist in predicting whether operating
Giacomo Fossataro is the technical and operation manager
equipment is fit for its intended service. The studies predict how at Walter Tosto with global responsibility for design, manufacturing
the material will behave according to certain operating conditions and quality control activities. He started his professional career in
and is used to establish an MPT curve. This curve provides an Walter Tosto’s technical department and has held many positions
accurate limit for operating characteristics. In this manner, startup within Walter Tosto including head of technical department and
manager of site activities. Mr. Fossataro holds a degree in engineering (industrial
and shutdown procedures can be set closer to these limits, making technologies) from the Politecnico di Milano.
the plant more flexible. If the MPT is under the curve, then we
are in optimal conditions. Other critical information necessary
to calculate the MPT include actual data from the material used. Michael De Colellis is a project manager at Walter Tosto
There is a direct correlation between the X and J factors and MPT. SpA in Chieti, Italy. He has a BE degree in manufacturing systems
The lower the X and J factors, the lower the MPT. And to achieve engineering from the University of Hertfordshire, UK, and an MSc
a low X and J factor, then cleaner materials with fewer impurities degree in advanced manufacturing systems and technology, from
the University of Liverpool. Mr. De Colellis began in the automo-
are necessary. Fig. 2 shows a typical MPT curve. tive and earthmoving equipment industry, working from quality engineer to quality
This field of research regarding the use of materials and pro- manager, at General Motors and Case New Holand, before transferring into the oil
cess standards for fabrication of heavy-wall vessels of 2¼ Cr- and gas pressure equipment construction business.
KPE
62
I FEBRUARY 2011 HydrocarbonProcessing.com
 CLEAN FUELS SPECIALREPORT

Designing atmospheric crude

distillation for bitumen service
Oil sands add complexity to separation units and require a new approach
M. GRANDE and M. GUTSCHER, Fluor Canada Ltd., Calgary, Alberta, Canada

B
itumen blends derived from the Alberta oil sands are becom- • Increased salt hydrolysis in the fired heater as desalting a
ing a significant feedstock for North American refiners. In dilbit feed has not been proven commercially reliable.
2009, Canada produced about 1.5 million bpd of raw bitu-
men with about 0.46 million bpd of bitumen blends exported to Processing issues. Processing bitumen blends, particularly
the US.1,2 This export figure becomes even larger when consider- dilbit containing Athabasca bitumen from the Alberta oil sands
ing bitumen blends that are commingled with conventional heavy that is the focus of this discussion, requires specific considerations
oil and are, therefore, classified as conventional heavy oil, such as that impact the design of a crude unit within an upgrader or the
Western Canadian Select (WCS). The steep production decline revamp of such a unit within an existing refinery. Revamp consid-
from Mexico’s Cantarell field and Venezuela’s recent shift toward erations may include existing crude units that will process various
non-US markets, such as China, could make securing supplies bitumen blends with other conventional feedstocks. In the case of
from Canada more attractive.3 Many US refineries in the Gulf an upgrader, this unit is often referred to as the diluent recovery
Coast area are already configured to process heavy oil and a pipe- unit (DRU) because the recovered naphtha/gas condensate is
line network is already established to transport oil sands produc- recycled as transportation diluent. Refiners processing dilbit or
tion to refineries located within Canada as well as in the US West, other feeds may also sell a portion of the recovered naphtha/con-
Midwest and Gulf Coast areas.1 Additional pipeline capacity has densate as transportation diluent as opposed to further refining
been recently completed to the US Midwest with additional pro- this material for the gasoline pool or as a petrochemical feedstock.
posals for other areas, including the Gulf Coast, indicating that Due to a shortage of diluent in Alberta in 2009, more than 60,000
more refiners will have access to feedstocks containing bitumen. bpd of diluent was returned to Alberta by rail from the US.1 The
completion of the Enbridge Southern Lights diluent pipeline will
BACKGROUND provide the capacity to deliver 180,000 bpd of diluent to Alberta
Bitumen from the Alberta oil sands has an extremely high from the US Midwest. Furthermore, with the use of the Capline
viscosity (typically approaching 1 x 106 cSt at 15°C) and a high pipeline, diluent from the US Gulf Coast area will be able to con-
asphaltene content approaching 20 wt% C5 insoluble. Conse- nect with the new Enbridge pipeline via the Chicap pipeline.1
quently, transportation of bitumen is accomplished by forming
blends with a diluent comprised of gas condensates or naphtha DRU COLUMN DESIGN
(C5+) that is termed dilbit, with synthetic crude oils termed syn- The main objectives of a DRU column are to recover transpor-
bit, or a combination thereof referred to as syndilbit. The blend- tation diluent remaining in the column feed (after preflash) and to
ing ratio for dilbit is typically about 70:30 bitumen to diluent by fractionate distillates, such as atmospheric gasoil (AGO), from the
volume; whereas for synbit, the blending ratio is typically 50:50. bitumen feed that can be processed directly in a hydroprocessing
These blending ratios are based on meeting pipeline specifications unit. To achieve these objectives, a typical column configuration, as
of 18°API and 350 cSt. Bitumen from the Alberta oil sands is shown in Fig. 1, consists of a diluent rectification section, an AGO
similar in gravity but typically much more viscous than the “extra pumparound section, an AGO product-side stripper, an AGO
heavy oil” produced from Venezuela’s Orinoco Belt. wash section and an atmospheric residue (AR) stripping section.

Challenges with bitumen. Some other challenging proper- Naphtha rectification section. The degree of fractionation
ties of bitumen from the Alberta oil sands include: required between the recovered naphtha in the DRU column
• Higher fouling tendencies and a lower thermal stability than overhead and the AGO product is dependent on whether the
other higher hydrogen-content crudes due to a high aromatic con- recovered naphtha will be further refined or will be returned as
tent, particularly asphaltenes transportation diluent. If the recovered naphtha is further frac-
• Large atmospheric residue (AR defined as 343+°C TBP) con- tionated and refined, the downstream naphtha processing units
tent of approximately 85 vol% will determine the naphtha endpoint and the sharpness of frac-
• High total acid number (TAN) value of approximately 2.5 to 3.5 tionation required. When the recovered naphtha is returned for
mg KOH/g, a high sulfur content of approximately 4.5 wt% to 5 wt%, transportation purposes, the degree of fractionation between the
and a high nitrogen content of approximately 0.3 wt% to 0.55 wt% recovered naphtha and the AGO product is typically determined
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 63
 CLEAN FUELS
HERMETICALLY SEALED
SUBMERSIBLE PUMPS
based on the percentage of diluent recovery desired while main-
taining a total recovered diluent composition that is essentially the
Not the length is important … same as the originating feed diluent, i.e., provide sufficient frac-
tionation gap between the diluent and the AGO products. As the
…but the technique initial boiling point of bitumen typically resides in the kerosine
boiling range, providing this fractionation gap is easily achievable
■ Abstain based on the typical boiling range of transportation diluent.
from drive shafts being long and susceptible to troubles If the naphtha is recycled for use as transportation diluent, the
■ Spare recovered naphtha from the DRU column overhead, together
needless shaft and guide bearings
with that of the preflash section, is typically routed to a reboiled
stripper to remove hydrogen sulfide (H2S) and other light mate-
■ Forget rials. The level of H2S stripping is dependent on the amount of
complex and cost-intensive seal technology cracked H2S formed in the fired heater and is a function of the
feed sulfur content and film temperatures reached in the fired
■ Require
heater. Significant diluent losses to the overhead of a stripper may
best available technology for a long service life be incurred if a stringent vapor pressure specification also applies.
and high availability For these cases, the recovered naphtha may be processed through
a refluxed column (i.e., a debutanizer) that will also achieve the
required H2S specification. The rectification section of a refluxed
column ensures that a high diluent recovery is maintained.

AGO PA and product stripping. The AGO pumparound

(PA) section removes a significant portion of cooling duty lower
in the column to help condense the AGO product and the AGO
wash oil sent to the wash section. The heat removed in the AGO

Preflash vapor
Offgas

Recoverd
Sour water naphtha
if 2 or 20 meters – we are flexible

support and Stripping

steam AGO product
cable pipe
Stripping
steam
pressure / AR product
discharge line Column feed
from fired heater

FIG. 1 Typical DRU column configuration.

extremely short
drive shaft 20 120

15 114
Fired heater COT, COTMax +/- °C

10 108
Diameter DBase, %

COT
5 102

0 96

-5 90
Diameter
-10 84

-15 78
25 35 45 55 65 75 85
Diluent preflash diluent feed, %
HERMETIC-Pumpen GmbH ™ P.O. Box 1220 ™ D-79191 Gundelfingen
[email protected] ™ www.lederle-hermetic.com FIG. 2 Impact of diluent preflash on fired-heater COT and column
diameter.
KPE
Select 171 at www.HydrocarbonProcessing.com/RS
64
 CLEAN FUELS SPECIALREPORT

PA section reduces the vapor traffic and the resulting required the preflash for a fixed AGO yield. Trays are best suited to achieve
column diameter of the diluent rectification section while pro- multiple stages of fractionation in this section.
viding higher heat recovery than that available from the col- The bottoms stripping section requires a smaller diameter rela-
umn overhead. The AGO withdrawn from the DRU column is tive to the upper sections based on the steam and stripped hydro-
steam stripped in a product side stripper for flash point reduction. carbon vapor loading. However, to minimize column height, using
The TAN content of the AGO material is typically about 2 mg a full-diameter sump is more practical for providing the required
KOH/g. This TAN content requires upgraded metallurgy for this AR product residence time. An internal cylinder may be utilized
column section, as well as for the hot portions of the AGO PA with multi-pass trays (preferably two-pass) that minimize liquid
and product circuits. stagnant zones with suitable active and fractional hole areas that
will minimize fouling and maximize tray efficiency.
AGO wash section. The degree of fractionation required
between AGO and AR products is based on the desired distillate PREFLASH TARGET CONSIDERATIONS
yield and endpoint specification (ASTM 95% temperature). The Due to the large amount of transportation diluent in the dilbit
yield of AGO and its associated endpoint is determined by the feed, a preflash system is often applied. The preflash removes a
level of distillate hydrotreating required to meet distillate product substantial portion of this diluent to lower the flow through the
specifications while minimizing AGO material in the AR product. remaining preheat circuit and the fired heater, as well as to reduce
The objectives of the wash zone are to minimize AGO product the DRU column diameter.
endpoint by rectifying the flash zone vapor, and to de-entrain AR The main process parameters involved in achieving distillate
in the flash zone vapor. Minimizing the endpoint for a desired lift are diluent slip (diluent that is remaining in the column feed),
yield will improve the quality of the AGO product that is fed to a stripping steam and fired-heater duty at the permissible COT.
hydroprocessing unit. The wash section also minimizes the amount Diluent slip and stripping steam assist in stripping distillate mate-
of solids/ultra fines, which can be particularly troublesome with rial in the bitumen feed that allows for a lower fired-heater COT or
mined bitumen feedstocks, from entering the AGO product draw. an incremental gain in AGO yield. The fired-heater COT required
The selected wash-oil rate and design of wash section internals for reliable operation in bitumen service is typically lower than that
is important to ensure that the listed objectives are achieved. encountered when processing light conventional crudes.
The wash-oil rate should be based on the governing require- Consequently, optimizing the preflash target requires assessing
ment between the required rectification for the AGO endpoint the impact that the diluent slip and stripping steam rate have on the
specification and the required overflash for de-entrainment of AR/ fired-heater COT and column diameter. This assessment should
solids. Overflash is defined as the true reflux, excluding entrained also include the costs associated with producing the steam required
liquid that exits the wash section. Good fractionation between and treating the resulting sour water produced. These concepts in
the AGO and AR products is best achieved with a combination optimizing the preflash section can also be applied to the revamp
of a low specific surface area (grid) type packing that is placed as a of an existing crude distillation unit (CDU) to unload the upper
bottom layer followed by a higher specific surface area (structured) portions of the column and column-overhead system. These areas
type packing as a top layer. The resulting combination improves may become bottlenecks due to the high naphtha content of dilbit
the de-entrainment and fractionation ability while maintaining a feeds even with preflash processing schemes.
reasonable packed-bed height and minimizing fouling. The larger
open area (relative to trays) also allows packing to better handle Column diameter assessment. The impact that the
a sudden increase in vapor rate, such as an upset that can occur if diluent preflash has on the DRU column diameter and fired-
a liquid water slug is carried over in the feed to the fired heater. heater COT is illustrated in Fig. 2 This figure is based on the
column configuration discussed earlier with a fixed stripping
Bottoms stripping. Bottoms stripping improves the frac- steam rate as well as a fixed AGO yield and endpoint specification.
tionation between AGO and AR products and allows for decreas- Fig. 2 illustrates that the fired-heater COT is reduced as
ing the fired-heater coil outlet temperature (COT) or increasing diluent preflash decreases at a fixed stripping steam rate. However,

20 120 3.6 120

Steam rate
15 114 3.3 114
Fired heater COT, COTMax +/- °C

Stripping steam rate, wt% AR

10 108 3.0 108

Diameter, % DBase
Diameter DBase, %

Diameter
5 102 2.7 102

0 96 2.4 96

-5 90 2.1 90
COT
-10 84 1.8 Diameter 84

-15 78 1.5 78
1.25 1.75 2.25 2.75 3.25 3.75 4.25 25 35 45 55 65 75 85
Stripping steam rate, % AR Diluent preflash, % diluent feed

FIG. 3 Impact of stripping steam rate on fired-heater COT and FIG. 4 Impact of diluent preflash and stripping steam on column
column diameter. diameter.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 65
SPECIALREPORT CLEAN FUELS

this reduction is obtained at the expense of significantly increasing This figure is based on the column configuration discussed earlier
the column diameter due to the additional diluent feed (vapor with a fixed AGO yield and end-point specification.
traffic) to the column. Fig. 4, as expected from Figs. 2 and 3, illustrates that column
The higher (and lighter) content of diluent in the column feed diameter is reduced when diluent preflash is maximized. This
provides marginal incremental lift with single-stage separation trend is observed up to a preflash value of approximately 80%.
that occurs in the flash zone. This single-stage separation, coupled At this high level of preflash, limitations of the overhead system
with the resulting relative volatility of the diluent mixture, does to maintain column reflux and a margin above water dew point
not effectively reduce the required fired-heater COT when the become a concern. For a two-stage condensing configuration (as
resulting impact on column diameter is considered. Consequently, shown in Fig. 1), as the amount of preflash increases, the hydrocar-
fired-heater designs that allow for an incrementally higher COT bon flowrate at the column overhead decreases and the steam rate
while maintaining suitable film temperatures and residence times increases. This combined effect significantly increases the steam
will significantly reduce the required column diameter due to the partial pressure, which reduces the amount of condensable material
allowable diluent reduction in the column feed. available for column reflux at a fixed condensing temperature. At
Achieving this incrementally higher COT may also have a sig- a diluent preflash of about 80%, the net overhead liquid product
nificant impact when considering the revamp of an existing CDU. available from the reflux drum is fully consumed by the reflux
Any modifications to the fired heater that will achieve a higher requirement. To increase preflash beyond 80%, the reflux tempera-
COT will allow for a higher preflash (practicality needs to be deter- ture must be reduced and/or AGO PA duty must be shifted to the
mined on a case-by-case basis). This higher preflash will unload the overhead system. Reducing the reflux temperature is not desirable
upper portions of the column and column-overhead system that as this quickly eliminates any margin between the reflux tempera-
may result in a higher dilbit feed throughput to the existing unit. ture and the water dew point temperature of the column overhead.
The impact that the stripping steam rate has on column diame- This reduced reflux temperature may lead to water condensing in
ter and fired-heater COT is illustrated in Fig. 3. This figure is based the first-stage overhead drum. Shifting the PA duty to the overhead
on the column configuration discussed earlier with a fixed-column condenser increases the vapor traffic in the naphtha-rectification
feed diluent content as well as a fixed AGO yield and endpoint section, which will increase the required column diameter, revers-
specification. Fig. 3 illustrates that the fired-heater COT is signifi- ing the trend of increasing preflash. Furthermore, shifting the PA
cantly reduced as the stripping steam rate increases. Furthermore, duty reduces the amount of high-level heat that can be recovered
the corresponding column diameter increase is not as significant from the column through heat integration.
as that required to achieve the same effect by increasing the diluent
content in the column feed (see Fig. 2). The stripping steam pro- PREFLASH TARGET OPTIMIZATION
vides more incremental lift due to its higher relative volatility and Considering the impact that preflash has on the DRU column
multiple stages of fractionation provided in the stripping section. diameter, the overall preflash target can be optimized with the
Another advantage that the stripping section stages provide remaining unit capital and operating costs. This optimization
is sharper fractionation between the AGO and AR products. should consider the cost of steam required for stripping, the
Consequently, the combined vapors from the stripping and flash operating cost to treat the resulting produced sour water and any
sections require less rectification in the wash section. If the wash- environmental issues/limitations in water usage.
oil rate is dictated by the AGO endpoint (i.e., the rectification The preflash target will also have implications on the heat-inte-
requirement discussed earlier), the required wash-oil rate will gration scheme. As the diluent preflash is increased, the preheat
decrease. This decrease will further lower the required fired-heater temperature required for preflash can increase significantly. For
COT because less bitumen material needs to be lifted to supply the example utilized in the earlier figures, the preheat temperature
the required wash-oil rate. required for a total diluent preflash of 55% is 185°C and increases
The disadvantage of significantly increasing the stripping to 235°C for a total diluent preflash of 80%. These temperatures
steam rate is the increased operating costs associated with supply- are at the second stage of a two-stage preflash drum configuration.
ing steam and treating the additional produced sour water. Fur- The preheat temperature(s) required to achieve the desired pre-
thermore, the water dew point of the column overhead increases flash can have a significant impact on the heat-recovery arrange-
and needs to be addressed in the design of the overhead system. ment and on the utility heat and/or fired heater duty. Therefore,
With the fired-heater COT set to the constraint established, the resulting heat integration scheme, including the cost benefits
the required column diameter vs. diluent preflash and stripping of using utility heat and the desired flexibility in preheat/preflash
steam rate may be determined. Fig. 4 illustrates this relationship. control, should be considered.

Single-stage preflash system Two-stage preflash system Preflash configuration. The preflash
target may be achieved with either a single-
Preflash vapor Preflash vapor
or multiple-stage preflash configuration, as
illustrated in Fig. 5. A preflash column is
Dilbit Column Dilbit Column not generally required due to the significant
feed feed feed feed volatility gap between the portion of trans-
portation diluent preflashed and the bitu-
men. Preflash drum(s) will provide adequate
separation within the range of preflash levels
presented in the earlier examples without
FIG. 5 Preflash configurations. impacting the desired fractionation between
the diluent and the AGO products.
KPE
66
I FEBRUARY 2011 HydrocarbonProcessing.com
 CLEAN FUELS SPECIALREPORT

To minimize fouling and provide reliable parallel flow control single-stage system. These reductions are achieved at the expense
for multiple heat-exchanger services and fired heater, single liquid of adding a second-stage flash drum and pump. The intent is to
phase dilbit preheat is desired. Single-phase dilbit preheat should reduce cost with the reduction in heat-exchanger design pressures
be maintained through to the inlet of the preflash flow control and piping flange ratings permitted by a two-stage configuration.
valve(s) and the inlet of the fired-heater pass control valves. To Fig. 6 illustrates the reductions in vapor pressure achievable
suppress vaporization at the required preheat temperatures, an with a two-stage system by plotting the resulting vapor pressure
adequate pump head must be supplied with the dilbit control vs. the desired preflash with a single- and a two-stage flash-drum
valve(s) placed at the back (i.e., hot) end of the preheat circuit(s), configuration. For the two-stage configuration, the first-stage flash
immediately upstream of each stage of preflash. is maintained constant with the objective of only removing all free
water resulting in a first-stage preflash of approximately 27%. To
Design. Dilbit feeds contain water and light-diluent compo- achieve the total desired preflash, any additional diluent flash is
nents that significantly increase the feed vapor pressure (par- generated with the second stage.
ticularly water). To achieve higher levels of preflash, the required
preheat temperatures increase, resulting in very large increases in 4,000
Single stage
the feed vapor pressure. An advantage of the two-stage configu- 3,500
ration is that the desired total preflash can be controlled at the
3,000
second stage, allowing the first-stage preheat temperature to be

Vapor pressure, kPaA

selected independently of the total desired preflash. The preheat 2,500
temperature for the first stage can be selected with the objective
2,000
of only removing all of the free water normally present in the feed,
thereby minimizing the vapor pressure of the first stage. 1,500 Second stage
Minimizing this vapor pressure will minimize the result- 1,000
ing operating pressure required to suppress vaporization in the First stage
first-stage preheat circuit. The desired total preflash is then fully 500
accomplished in the second stage at a comparably lower vapor 0
pressure than that required with a single-stage configuration. 25 35 45 55 65 75 85
Diluent preflash, % diluent feed
Consequently, the head requirement of the preflash feed pumps
as well as the design pressures of downstream exchangers/piping FIG. 6 Effect of diluent preflash on vapor pressure.
in both stages for a two-stage system are reduced compared to a

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SPECIALREPORT CLEAN FUELS

Fig. 6 illustrates that the resulting exchanger design pressures, A higher than expected feed-water content will affect the per-
piping flange ratings and combined pump-head requirements for formance of the preflash section and column overhead system
the single-stage preflash configuration become much greater than for both preflash configurations. A higher feed-water content
for the two-stage configuration as the diluent preflash increases. will alter the preflash temperatures and may affect the amount
Consequently, a two-stage configuration may become more of diluent preflashed. The additional steam entering the column
appealing for higher levels of diluent preflash. For integrated mine- overhead system from the preflash section may increase the over-
upgrader facilities, where higher unit feed dilbit ratios are encoun- head system pressure, increase the offgas rate (resulting in lower
tered, it may be desirable to achieve a much higher diluent preflash diluent recovery and possible venting to the flare) and signifi-
to maintain a similar optimum diluent slip to the DRU column as cantly increase sour-water production that could accumulate in
in a segregated upgrader/refinery facility. Therefore, a multi-stage the overhead drum. These consequences for the preflash section
configuration is even more appealing for integrated mine-upgrader and column overhead system should be evaluated to determine
facilities than for a stand-alone refinery or upgrader. if design adjustments to minimize these impacts are warranted.

Free water issues. Free water that is not removed from a DRU COLUMN OVERHEAD SYSTEM DESIGN
diluted bitumen feed may cause significant damage to the fired The objectives of the overhead system are to condense the
heater and/or to the DRU column due to the heater’s ability to DRU column overhead and preflash overheads; supply column
rapidly vaporize the free water. At the very least, if water is unex- reflux; and separate water and any noncondensable gases present
pectedly present at the heater inlet control valves, it will likely form due to cracking reactions (thermal decomposition) in the fired
steam, thus creating two-phase flow and control difficulties with heater. Design of the overhead system should mitigate corrosion
the heater pass control valves. Consequently, a two-stage preflash to maximize equipment service life while providing an operation-
configuration that removes all feed water in the first-stage flash ally reliable design. HP
offers an additional benefit. With this design, should a slug of feed Extended version avaiable online at HydrocarbonProcessing.com.
water enter the unit, the second-stage flash will reduce the risk of
free water breaking through to the final preheat circuit upstream Marco Grande is a principal process engineer with Fluor Canada Ltd., Calgary,
of the fired heater. However, both single- and two-stage preflash Alberta, Canada. His experience is in bitumen/heavy-oil upgrading and downstream
configurations that are designed for a high level of diluent preflash refining. He holds a BSc degree in chemical engineering from the University of Alberta.

(i.e., hotter preflash temperatures) will operate with a margin above Matthew Gutscher is an engineer in training (EIT) in the process engineering
the expected water dew point and will consequently provide some group with Fluor Canada Ltd., Calgary, Alberta, Canada. He has a BSc degree in
flexibility in removing a higher than expected feed-water content. chemical engineering from the University of Alberta.

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 CLEAN FUELS SPECIALREPORT

Minimize carbon footprint

from Claus tail-gas units
Reevaluate emissions efficiencies on sulfur-removal operations
M. P. HEISEL, ITS Reaktortechnik GmbH, Pullach, Germany; and
M. RAMESHNI, Worley Parsons, Monrovia, California

T
here are thousands of sulfur recovery units (SRUs) world- For other energy forms, equivalents must be calculated by more
wide converting poisonous hydrogen sulfide (H2S) into ele- complex methods, as summarized in Table 1.
mental sulfur (S). A typical two-stage Claus plant achieves All of these values are calculated rather conservatively. For
95%–97% recovery. In most cases, secondary tail-gas treating is example, generating electric power in a lignite-fired power plant
required for total recoveries from 98% to 99.98%. requires more CO2 than in a gas-power plant and that too does
In the past, authorities required a sulfur recovery rate (SRR) not have more than approximately 40% efficiency. Actually, per
to meet local legislation. Other emissions, notably carbon dioxide kWh electric power, one can assume between 439 g CO2 /kWh
(CO2), were of no concern. In view of the global climate change and 1,306 g CO2 /kWh (see Fig. 1), which corresponds to 0.22
debate and continuously rising energy prices, limiting CO2 emis- m³ CO2/kWh to 0.65 m³ CO2/kWh. For our calculation, we
sion is becoming important. Various Claus tail-gas treatment assumed 0.26 m³ CO2 /kWh, i.e., a low value.
options are available, but, differ in terms of carbon footprint,
sulfur recovery efficiency, capital expenditure (CAPEX) and oper- The processes. The basic principle of the Claus process is the
ating expenses (OPEX).
What is the best? There are three principles of Claus tail-gas 1,400
treatment:
GHG, grams CO2 equialent/kWh

1,200 Indirect, from life cycle

289 Direct emissions from burning
• Recycle processes that convert all residual sulfur species
1,000 Twin bars indicate range
into either H2S or sulfur dioxide (SO2) scrub off this species and 176
recycle it to the front end of the Claus plant 800
• Cyclical catalytic sub dew point (SDP) processes that con- 600 113
tinue the Claus reaction at temperatures below the SDP and shift 1017 77
400 790
the chemical equilibrium to more sulfur formation 575
• Selective oxidation of H2S directly to elemental S. 200 362
236 280
4 48 10 21
In quantifying relative CO2 emissions, it is surprising how 0 100 9
Coal Gas Hydro Solar PV Wind Nuclear
much the carbon footprint can vary between processes despite Source: IAEA 2000
comparable sulfur recovery efficiencies as presented here.
FIG. 1 CO2 emission per kWh of electric power.1
Calculation method. Barring sister units, there probably are
not two really identical Claus plants in the
world, even though the process principle To atmosphere
is very similar. For example, there are dif-
MP stream W1 W2 MP stream
ferent methods of reheat before entering
the catalytic reactors, as indirect heating by F1 F2
steam or by inline burners, to name just two Feed gas
C1 R1 R2
alternatives frequently applied. When com-
paring available processes, a base case must Oxygen BFW BFW
be selected. The calculation method is listed (optional)
so that every adaptation of the specific case W3 W4
can easily be done.
Quantitative comparison requires defin-
ing an equivalent unit of CO2 emission for
Air Sulfur Air Fuel gas
any form of energy expended. This is easiest
done via fuel gas, where oxidation of 1 mole FIG. 2 Typical process flow diagram of a 2-stage Claus plant.
of methane (CH4) emits 1 mole of CO2.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 71
SPECIALREPORT CLEAN FUELS

TABLE 1. Basic data for calculation of CO2 footprint

Thermal energy 1 m³/h of CH4 generates 35,200 kJ/h which is 9.78 kWh/h. With this value can be calculated the CO2 emission of thermal sources, e.g., of steam
Electric power 1 kW electric power was assumed to be generated from thermal power with an efficiency of 40% which results in
9.78 x 40% = 3.76 kWh/m³ CO2 or 0.26 m³ CO2/kWh
N2 Requires approximately 0.2 kW/m³ which results then in 0.2 / 3.79 = 0.05 m³ CO2
Instrument air Compression energy to 10 bar plus 10% for purification: 0.15 kWh/m³ = 0.15/3.79 = 0.06 m³ CO2
Cooling water Pumping energy up to 20 bar = 0.75 kWh/m³ = 0.2 m³ CO2 /m³ CW
Demin water Cooling water + 20% = 0.24 m³ CO2 /m³ demineralized water
HP steam Requires thermal energy of 1,678 kJ/kg steam (45 bar) plus preheat of boiler feed water from ca 105°C to boiling temperature
of 256°C = (1,685 + 417) / 35,200 = 0.06 m³ CO2
LP steam Requires thermal energy of 2,119 kJ/kg steam (4.5 bar) = 2,119/35,200 = 0.06 m³ CO2

TABLE 2. Process data for calculation

Air Air
Claus capacity 100 t/d sulfur
Claus feed Feed composition See Table 3
gas Claus Direct Vent gas
Incinerator Reheat HP steam, indirect
plant oxidation
Air1, Air2, Air3 Dedicated blowers for each of these units
Air demand analyzer H2S /SO2 ratio = 6
Sulfur Sulfur Fuel Temperatures See Table 3
FIG. 3 Block diagram of direct oxidation tail-gas treatment.
tially a power house, generating steam from oxidation of H2S
to elemental S with very little CO2 emission. In the majority of
Claus plants, the feed gas has a CO2 content of less than 10 vol%.
Claus furnace Claus sections ½ Direct Incinerator
oxidation The incoming CO2 is of course later emitted from the plant. In
Selective addition, the fuel gas is consumed to thermally oxidize residual
Claus oxidation Claus tail-gas sulfur species to SO2. This fuel gas also adds to the
Reheater reactor reactor Stack CO2 emission. Overall, a Claus plant produces a lot of steam with
Steam very little CO2 emission. Actually, H2S is a very potent fuel with
Incinerator zero CO2 footprint of its own. Unfortunately, it has the great
Waste-heat Steam
boiler disadvantage that its incineration product SO2 is very poisonous.
QC QC Of course, the heating capacity of the Claus process can be used
Combustion in an industrial complex, thus reducing fuel requirements and
chamber CO2 emissions elsewhere.
Condenser The two-stage process does not meet current environmental
S S S S requirements. Therefore, tail-gas treatment processes are added
H2S 0.8–1.5 vol% downstream for improved sulfur recovery. There are three types
FrC FC of tail-gas treatment processes—selective direct oxidation, the
O2 0.5–2 vol% recycle processes and the SDP—and these will be discussed here.
Feed gas Air
Direct oxidation processes. In a direct oxidation process,
FIG. 4 Typical process flow diagram of a direct oxidation the Claus reaction furnace is operated slightly air-deficient so that
process.2 the tail gas contains mainly H2S that is then directly oxidized to
sulfur with supplemental air, as shown in Fig. 4. Tail-gas H2S must
conversion of H2S into elemental S. In a two-stage Claus unit, typically be limited to 1.5 vol% to avoid catalyst damage from
this is done by oxidation of nominally one-third of the H2S in high exotherms. As a matter of practicality, three Claus stages are
the feed gas to SO2 and reacting these compounds according to advisable to temper the impact of real-world fluctuations.
the Claus equation: To calculate the CO2 footprint from the direct oxidation
2 H2S + 1 SO2 Ù 3/x Sx + 2H2O + energy Claus reaction process, data from Table 2 was applied. With the data listed in
Tables 1 and 3, the CO2 footprint can be calculated. Table 4
x: 2, 4, 6, 8 according to the modifications of sulfur summarized the results (Editors note: Table 3 is available online
This reaction initially takes place in the Claus furnace, typi- at HydrocarbonProcessing.com).
cally accounting for 60%–70% of total conversion. This level is The process generates more energy than it consumes. This
not sufficient to meet environmental standards, and the reaction results in a carbon credit from surplus energy. In the tables, this
must proceed further in downstream catalytic stages. A two-stage is indicated by negative CO2 emission numbers. For the other
Claus plant typically achieves 95%–97% sulfur recovery. A typical tail-gas treatment processes, the same calculating system for deter-
process flow diagram is shown in Fig. 2. mining the CO2 footprint was applied. However, it is not shown
From a carbon footprint perspective, the Claus process is essen- in the same extent of details as in this example.
KPE
72
I FEBRUARY 2011 HydrocarbonProcessing.com
 KPE
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SPECIALREPORT CLEAN FUELS

H2S recycle
TABLE 4. Summary calculation of CO2 footprint
Air
of Claus unit plus direct oxidation tail–gas treatment
Claus Vent Import Equivalent CO2 emission
feed gas Claus Hydrogen- H2S gas
Incinerator El. Energy, kW 456 120
plant at ion wash
Cooling water, m³/h 0 0
H2, std m³/h 0 0
Sulfur Fuel Fuel, std m³/h CH4 335 335
FIG. 5 Block diagram of hydrogenating recycle process. Instrument air, std m³/h 90 3
N2, std m³/h 0 0
Demin. water, m³/h 18 4
Claus unit To incinerator HP steam, 45 bar sat t/h 3.32 220
offgas Heat
1 LP steam, 4.5 bar sat t/h 0.2 13
recovery
Lean amine Export
from regen.
2 4 5 HP steam, 45 bar sat t/h 8.48 –562
Reducing Partly loaded LP steam, 4.5 bar sat t/h 5.69 –377
gas (opt.) amine to
regenerator SRR,% 98.60
or another SO2 emission, m³/h 40.9
3 Air or absorber
CW SO2 emission, kg/h 116.7
CO2-emission total, m³/h –244
Water (to utilities CO2-emission total, kg/h –479
or disposal)
In a sulfur condenser, the sulfur is recovered and the inert gas
recycled to the reactor. While the catalyst regeneration is proceed-
Upstream (shown as block “1”), Claus furnace and catalytic Claus sections 1
and 2 shown, Hydrogenation step “2” cooler “3”, quench “4”, amine scrubber ing, a parallel SDP reactor takes over the task.
“5”, downstream (not shown), Regeneration and incinerator. There are several processes applying this principle—SDP1, SDP2
FIG. 6 Typical PFD of a hydrogenation tail-gas treatment.2 and SDP3.a,b,c SDP1 was chosen here for the comparison. The oth-
ers can easily be derived from the SDP1 data. For calculation of the
CO2 footprint of the SDP1 process, Table 5 summarizes the data.
Recycle processes. Fig. 5 shows a typical hydrogenating For the regeneration cycle, the data in Table 5 were assumed. Table
recycle process. In such a process, the Claus tail gas is catalytically 6 lists results from the CO2 footprint calculation. SDP1 produces
reduced to convert virtually all sulfur species and sulfur vapor to more energy from the conversion of H2S to elemental S than it con-
H2S, which is then absorbed in an amine scrubber. Usually, a ter- sumes. Therefore, the net CO2 emission from the process is negative.
tiary amine selective for H2S is used to limit CO2 co-absorption to
approximately 15%. In the regeneration column, a concentrated Alternative SDP processes. The process principle of SDP4
H2S fraction is stripped off and is recycled to the front end of the is a combination of a conventional Claus process with the well-
Claus plant, as shown in Fig. 6 (Editors note: Figs. 7–9 are avail- proven sub-dew-point tail-gas treatment, as the SDP1 and SDP2
able online at HydrocarbonProcessing.com). processes.a,b,d Unlike these older processes, SDP4f combines the
There are many possible process variations. In particular, the Claus furnace with just two catalytic reactors, which are cooled
hydrogenation bed is often filled with a low-temperature hydro- internally. This allows sulfur recovery efficiencies up to 99.85%.
genation catalyst now commonly used to reduce preheat energy, Such high values could be achieved in the past only by much
thus reducing CO2 emissions by approximately 10%. For the more complicated processes, i.e., a complete Claus plant with
comparison, we chose a conventional catalyst requiring higher downstream tail-gas treatment. As the two-reactor process requires
inlet temperatures. The calculation method and process data less equipment and process steps, it is cheaper and more reliable.
applied are the same as for the direct-oxidation process with only Equipment that is not there cannot fail. Fig. 10 is a simplified
one exception: In the air-demand analyzer (ADA), the H2S/SO2 process flow diagram.
ratio is 2 here, while it was 6 for direct oxidation. Table 6 sum- The fundamental idea of SDP4 is removing reaction heat
marizes the results of the CO2 footprint calculation. of the Claus reaction directly in the catalyst bed rather than in
a downstream heat exchanger. This controls the temperature
SDP processes. For the SDP process, the catalytic Claus reac- throughout the catalyst bed within a narrow range. The top layer
tion is continued at lower temperatures, which shifts the chemi- of the catalyst is left without cooling. The feed temperature to
cal equilibrium to favor more sulfur formation. The tempera- this adiabatic section is typically 220°C and reaction heats it up
ture is chosen between the sulfur solidification point at 120°C to 320°C—the temperature required for COS and CS2 hydrolysis.
and the SDP, which, in practice, means an inlet temperature of The second section downstream in the same reactor is cooled to
125°C–130°C. During operation, the reactor operated at SDP an outlet temperature of typically 260°C. This combination of
conditions accumulates condensed sulfur which slowly deactivates adiabatic and cooled reaction reaches conversion rates comparable
the catalyst. It therefore has to be regenerated, which is done by to a two-stage Claus plant.
taking this reactor out of operation and heating it by an inert gas, Downstream then follows a sulfur condenser and then a second
such as nitrogen (N2), to vaporize sulfur deposited on the catalyst. identical reactor which, is operated at lower temperatures. This
KPE
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SPECIALREPORT CLEAN FUELS

TABLE 5. Data for calculation of energy demand for

Air 4 Air Fuel regeneration of the sulfur loaded SDP1 reactor
Reheat
Inert gas N2
9 Reheat
3
Claus Gas flow 250 kmol/h
furnace Incinerator Temperature in sulfur condenser 125°C
1 5 10 1 Regeneration temperature 340°C
2
⌬t in heat exchanger, which has to be covered by fuel 30°C
Feed 6 11
gas 8
SDP4 SDP4 TABLE 6. Comparison of the CO2 and SO2 footprints of
stage Sulfur stage
hot mode condenser various Claus tail-gas treatment processes
cold mode
7 Import Claus 1 Claus 2 SDP1 SDP4 SDP5 SDP6
Equivalent CO2 emission, m3/h
kW 189 120 140 135 119 124
FIG. 10 SDP4 process flow diagram.
Cooling water, m3/h 80 0 0 0 0 0
H2, m3/h 42 0 0 0 0 0
Fuel, std m3/h CH4 384 335 323 356 262 297
Air Air
Instrument air, std m3/h 3 3 3 2 3 3
Claus Vent N2, std m3/h 6 0 3 0 0 0
feed gas Claus Hydro- Selective Thermal gas Demin water, m3/h 10 4 4 4 4 4
plant genation oxidation incineration
HP steam, 45 bar sat, t/h 115 220 156 73 116 165
LP steam, 4.5 bar sat, t/h 179 13 13 13 13 13
Sulfur Sulfur Fuel Export
FIG. 11 Block diagram of the TGT5 process. HP steam, 45 bar sat, t/h –721 –562 –626 –864 –590 –579
LP steam, 4.5 bar sat, t/h –109 –377 –309 –195 –332 –309
SRR, % 99.9 98.6 99 99.8 99 97.3
SO2 emission, kg/h 8 117 83 13 81 224
SRU tail gas
Total CO2 emission, kg/h 349.6 –479.0 –577.5 –932.1 –798.1 –554.4
Natural gas Recycle Claus 1 r Hydrogenating (TGT1)g
water Claus 2 r Direct oxidation (TGT2)h
Combustion air Contact SDP1 r Sub-dew-point 1a
SDP4 r Sub-dew-point 4d
RGG condenser Sour water SDP5 r Hydrogenation/selective oxidation (TGT5)e
blowdown SDP6 r Catalytic incineration (TGT6)f
Hydrogenation
reactor Reaction heat in the catalytic converters generates steam. For
Steam Desuper-
heater the CO2 footprint calculation, it was assumed that this steam is
reheater
condensed in air coolers. This reduces the energy efficiency of the
Air process, but it simplifies operation. Table 6 summarizes the results
Reduced
TGT5 tail gas of the CO2 footprint calculation. SDP4 produces more energy
reactor 10% NaOH from the conversion of H2S to elemental S than it consumes on the
LP steam way. Therefore, the net CO2 emission from the process is negative.
Sulfur
condenser Tail gas to Hydrogenation/selective process. The TGT5 catalyst is a
incinerator proprietary low-temperature H2S oxidation and Claus-reaction
catalyst.e Reduced tail gas from the TGT5 contact condenser is
Sulfur reheated to 200°C–250°C and combined with a stoichiometric
FIG. 12 TGT5 process flow diagram.
quantity of air in the reactor to produce elemental S that is subse-
quently condensed. Total recoveries of 98.5%–99.5% are achiev-
able. The reactor inlet is limited to 5 vol% H2S, above which
shifts the chemical equilibrium toward more sulfur formation. Actu- recycle dilution (or inter-bed heat removal) is necessary to limit the
ally, the outlet temperature is chosen in the range of 100°C–125°C, exotherm. A simplified process flow diagram is shown in Fig. 12.
i.e., even below the S solidification point. In this operating mode, The result of the CO2 footprint calculation is summarized
sulfur recovery rates (SRRs) up to 99.85% have been observed. in the Table 6 overview. The SDP5 process also produces more
During the operation below the SDP, the sulfur produced accu- energy from the conversion of H2S to elemental S than it con-
mulates on the catalyst and deactivates it slowly. Therefore, the cata- sumes on the way. Therefore, the net CO2 emission from the
lyst must to be regenerated and that is done by switching it into the process is negative.
position of the first reactor. At high temperatures of up to 320°C, the Catalytic incineration process. For the increasingly rare
sulfur is desorbed and the catalyst regenerated. The former first reac- instances when tail gas treatment is still not required, a new pro-
tor is switched at the same time into the position as the cold second cess, TGT6, uses a two-stage catalytic thermal incineration process
reactor. This procedure is repeated typically once every 24 hours. (patent pending).f A low-temperature hydrogenation catalyst
KPE
76
I FEBRUARY 2011 HydrocarbonProcessing.com
 CLEAN FUELS SPECIALREPORT

TABLE. 7. CAPEX for various sulfur recovery processes

and their respective SRRs O2 To SO2
AC recovery
CAPEX in % of or stack
Plant type second-stage Claus unit SRR, %
2-stage Claus unit plus
incinerator (base case) 100 95–97 TGT6
SUPERCLAUS (downstream oxidation
catalyst
of a 3-stage Claus) 140–160 98.5–99.2
Hydrogenating tail
gas treatment, Amine 150–200 > 99.9 Low
Oxidation temperature
SDP1 130–150 99.0–99.4 hydrogenation
air blower
SDP4 140–160 99.4–99.8 catalyst
Supplemental
TGT5 130–150 98.5–99.5 hydrogen (optional)
TGT6 130 96.5–98 HP steam
Claus tail gas

converts virtually all Claus tail-gas sulfur to H2S while capital-

izing on the resultant exotherm to initiate thermal oxidation in FIG. 13 TGT6 process flow diagram.
the subsequent TGT5 stage. Incineration fuel is thus substantially
reduced from that required for conventional catalytic incinera-
tion. A simplified process flow diagram is shown in Fig. 13. Table
Michael Heisel PhD, is general manager of ITS Reaktortechnik GmbH. He has
6 summarizes the CO2 footprint calculation results. The TGT6 more than 30 years of experience in sulfur recovery plant design, startup, validation
process also produces more energy from the conversion of H2S to and troubleshooting.
elemental S than it consumes. Also, the net CO2 emission from
the process is negative. Mahin Rameshni P.E., is vice president and global manager – Sulfur Technology
& Gas Processing for Worley Parsons in Monrovia, California. She has more than 22
Comparing technologies. With the data from the described years of experience in the design of sulfur recovery and gas processing plants and
technologies, we can now compare the respective CO2 footprint holds six patents.

quantified. In Table 6, the CO2 contributions of the different

steps in the processes are listed. One can easily distinguish the
contributions of different forms of energy to the emissions.

Import of utilities. Needed imports include:

Electric power. While TGT2,h SDP1, SDP4 and TGT5 are
rather close together, TGT1g requires 50% more power. The reason
is mainly that the downstream scrubbing process has a consump-
tion to pump solvent around, which increases power requirements.
Hydrogen (H2). Only TGT1g and TGT5 reduce the sulfur
species to H2S, and, therefore, they are the only processes to
require some H2. With the new low-temperature hydrogenation
catalysts, H2 demand may approach zero.
Fuel. All processes require fuel to incinerate the offgas. The
different requirements result from varying compositions of the
tail gases. But, the total fuel consumptions do not vary widely,
with the exception of TGT5, which requires 10% less than TGT2,
SDP1 and SDP4, while TGT1 needs 20% more due to recycle
gas. In some TGT1 installations, the incinerator may be operated
in stand-by mode. This reduces fuel consumption.
High-pressure (HP) steam. This is required essentially for
reheating the process gas to the inlet of the catalytic reactors. The
more reactors there are, the more HP steam is required. In that
respect, SDP4 needs only 1⁄3 of TGT2 requirements. The HP-
steam consumption contributes markedly to the total consump-
tion of all the processes.
Low-pressure (LP) steam. All processes need some LP steam to
heat sulfur lines. TGT1 needs major LP steam quantities to regen-
erate the scrubber solvent. But all processes also produce LP steam,
so all generate a surplus of steam with the exception of TGT1. HP

Extended version avaiable online at HydrocarbonProcessing.com.

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77
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 GAS PROCESSING DEVELOPMENTS

Avoid these risks concerning

combustion control in fired heaters
Tuneable diode laser analyzers offer diagnostic benefits
R. JENKINS, Servomex, Crowborough, England

F
ired heaters are integral to hydrocarbon processing (HP). burners. Such conditions can lead to a number of negative process
Specifically designed for the reaction of fuel and air to pro- control conditions, including excess heat at the process tubes,
duce extremely high gas temperatures, heaters transfer this which causes damage and leaks; carbon deposits on the process
energy to potentially flammable process fluids via heat exchangers. tubes, which causes decreased efficiency and heat transfer; and, in
They consume large quantities of fuel, produce large quantities extreme cases, potentially dangerous combustion events.
of emissions, and are a potential safety hazard to personnel and However if a process problem is detected either by analytical
the plant. However, they are irreplaceable within hydrocarbon instruments or other safety devices, it is inadvisable to simply
processing—so they warrant the highest levels of understanding switch off the fuel supply to the burners. Abrupt stops, restarts
and care in their operation and control. and light-off conditions are the most common time for furnace
Recent improvements to reduce NOx emissions require closer incidences to occur. It is safer to bring the process carefully and
process monitoring, as newer burners often operate under nar- correctly under control than to fully shut down and restart the
rower process control conditions than older, larger-nozzle-diam- process, and this is why comprehensive analysis of the products of
eter gas burners. Demands have grown on plant operators to combustion, or the lack of them, is vital.
improve safety practices, increase plant efficiency and reduce Despite the risks, there are measureable rewards for operating
environmental emissions. As a consequence, accurate and reliable fired heaters at low excess-air (LEA) levels. In LEA combustion
instrumentation is required to support the control of the process. control, the lowest level of fuel is consumed and the combustion
Improved technologies are available to control fired-heater com- products are cooled the least by unused excess air. The cost ben-
bustion with greater accuracy and reliability, but the correct selec- efits of these efficiencies are considerable—just a single percentage
tion and effective use of these technologies require understanding saving in fuel can save hundreds of thousands of dollars per year.
of a complex and delicate process. Controlling air levels just above the point at which incomplete
combustion starts also enables the “cleanest burn,” helping plants
Principles of effective combustion control in fired meet emissions requirements. This, in particular, reduces the
heaters. The cornerstone of a well-controlled combustion pro- emission of NOx , created when unused O2 reacts with nitrogen
cess is optimized air-to-flue ratio and efficient fuel consumption.
Before analyzer technologies were developed to measure excess air
in the products of combustion, fired heaters were run in condi-
tions of high excess air. Although this meant inefficient and costly Fuel-rich
CO, combustibles NOx
fuel consumption, it was the only way to avoid the creation of and soot
low-oxygen, fuel-rich conditions that could lead to dangerous
explosions.
Zirconium oxide technologies that were introduced in the
late 1960s allowed engineers to obtain reliable and continuous Efficiency
measurements of excess air, enabling them to reduce the air-to-fuel
ratio closer to that of the theoretical stoichiometric combustion
mix. Unfortunately, reducing excess air poses a new problem: the Air-rich
Ideal
nearer the process moves to the tipping point at which incomplete O2
combustion takes place, the potential to move from safe to unsafe
operating conditions increases, as well as the speed at which these
transitions can happen (Fig. 1).
-3 0 3 6
The control and safety systems that run fired heaters must Excess oxygen, %
therefore perform an extremely complicated balancing act. It is not
enough to just increase excess air levels when incomplete combus- FIG. 1 Example of a gas-fired process; actual excess oxygen
tion is detected, as the complex interactions of O2 and unburned levels will vary with heater size, fuel, loading and ambient
fuel can lead to flammable mixtures igniting further down from the conditions.
KPE
HYDROCARBON PROCESSING FEBRUARY 2011
I 79
GAS PROCESSING DEVELOPMENTS

from the combustion air, which will be produced even by low compressed air or, occasionally, by nitrogen, which is used to
NOx burners if they are not run lean (Fig. 2). extract the sample from the process.
A competent LEA combustion process—running at approxi- As this type of system can be installed close to the burners,
mately 2.5%–5% excess air or 0.5%–1% O2 above the point at the lag time for analysis—the measurement delay due to sensor
which unburned fuel in the form of CO starts to break through— response—is minimized, giving operators a comparatively short
can be maintained and controlled at the most efficient running response time. Individual burner performance can be monitored
point. As soon as there is not enough air to allow full fuel combus- by installing multiple analyzers across banks of burners; this is
tion, the process will quickly degenerate into an unsafe condition. especially important in fired heaters where low NOx burners are
Pockets of CO and possibly hydrogen and methane can travel fitted, as the burners are notoriously difficult to evaluate through
through the process, causing localized hot spots as they ignite. visual inspection because the flame is nonluminous. Many systems
These effects begin to manifest at less than 10%–15% excess air or also offer the option of fitting an additional CO or combustibles
2%–3% O2 in the flue gas, with burner inefficiencies preventing catalytic sensor. This offers additional diagnostic benefits for pro-
stoichiometric combustion levels being reached. cess and burner optimization, including providing early indica-
Excluding extractive techniques used for portable gas analyz- tions that excess-air levels are too low, or that a bank of burners is
ers and some highly specialist fixed-gas analyzer applications, incorrectly set up, adversely affected by other burners or suffering
there are currently two very different technologies available to from nozzle blockage.
measure the level of unused O2 in the fired-heater combustion Flame traps should always be specified when choosing this
process. Zirconium oxide cell technologies—commonly known type of analyzer system to prevent the sensors from becoming a
as zirconia—have been established for more than 40 years, but source of ignition back to the process. Care should then be taken
have recently been challenged by the introduction of tuneable to ensure that the flame traps have little effect on measurement
diode laser (TDL) analyzers. Both offer distinct advantages and lag times. High-flow close-coupled extractive analyzers—analyzers
disadvantages in their usage, so it is extremely important to under- that aspirate over 1 L/min of sample from the process—can suffer
stand their respective qualities to deduce which is most suitable from considerable sample lag times, as the pressure drops across
for an application. Neither offers a “one-size-fits-all” solution, flame traps and causes a reduction in sample flow to the zirconia
but there are notable advantages to be gained by using them as sensor. For added measurement certainty, it is recommended that
complementary techniques. analyzers are specified where the calibration gases supplied to the
instrument can verify the whole system’s performance, inclusive
Zirconium oxide: Optimum techniques for optimum of the probe inlet to the analyzer, sensors and the aspirator outlet.
O2 control. Zirconia is a proven technology that measures O2 With in-situ analyzers, the zirconia sensor is situated at the end
on a wet basis, enabling the sampling and direct analysis from the of a probe that is inserted into the hot products of combustion.
hot, wet and often corrosive products of combustion. This avoids While relatively simple and cost-effective to install, the sensor
added complexities and reliability issues associated with a sample is directly affected by the process temperature variations and is
conditioning system. limited in absolute operational temperature. The mechanical
Zirconia analyzers are broadly split into two types: close-cou- requirements of higher-temperature operation—effectively mak-
pled extractive analyzers and in-situ analyzers. The most effective ing the analyzer operate like a diffusion-based, semi-close-couple
and reliable method for using zirconia technology in process extractive analyzer—are complex, with bulky assemblies that incur
control is within a close-coupled extractive analyzer system, where high installation overheads.
a sampling system and sensor enclosure is installed to the side of Critically, when flame traps are fitted to an in-situ technique,
the process. This enclosure is heated above the gas dew point and the lag time can be more than one minute in length which many
contains the zirconia sensor connected to the process via a sample engineers will consider too risky for safe control. Problems can be
probe. The enclosure normally contains an aspirator driven by compounded by probe installation points: if placed too far from
the burners to limit process temperature effects on the sensors,
then both air ingress into the flue and delays caused by distance
from the burners can weaken the ability to control the process
Convective heat
efficiently and safely. As a consequence, engineers must have a
Zirconia or irconia clear understanding that the processes may be compromised by
and combustibles
the potential shortcomings of in-situ techniques, regardless of the
initial installation cost benefits they offer.

TDL TECHNOLOGIES: A COMPLEMENTARY

Radiant heat
TECHNOLOGY TO OPTIMIZE PROCESSES
A major development in gas analysis techniques has been the
introduction of TDL technologies. Enthusiastically received by
engineers and plant operators, a range of different technology
integrations are now available from multiple manufacturers.
Yet, while TDL offers advantages in measuring multiple gas
TDL methane,
carbon monoxide Burner
types, it also has limitations that make its use in fired heaters a
and water complementary technique rather than a complete replacement
for other technologies.
FIG. 2 A typical cross-stack system consists of the laser-emitter
module and receiver mounted across the process pipeline or
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GAS PROCESSING DEVELOPMENTS

flue stack. The gas concentration information is held in the gas and can only be achieved by purging the dead space with a gas that
absorption line shape, which is obtained by scanning the laser will not interfere with the measurement. For an O2 measurement,
wavelength over the specific absorption line. The measured signal this precludes the use of compressed air, so nitrogen needs to be
intensity is detected by a photodiode and then used to determine used as the purge gas. As this is normally consumed at a rate of 20
the gas concentration. L/min to 50 Lmin, depending on process-gas velocity, it makes
There are primarily two cross-stack TDL technologies in use: operation prohibitively expensive when compared with zirconia
Direct absorption spectroscopy (DAS) and wavelength-modulated techniques unless the process is too corrosive or dust-laden for a
spectroscopy (WMS). DAS is the first-generation technique of zirconia analyzer to operate reliably.
TDL absorption spectroscopy, providing measurements from a TDL delivers greater advantages in the measurement of CO,
relatively crude approximation of the area under the absorption with the fast response and specificity of TDL enabling CO break-
curve generated by the laser scan. Today, few analyzer manufac- through to be monitored accurately. While it is not generally
turers use this approach to measurement analysis, as DAS yields advisable to use CO breakthrough as part of the process-control
a relatively noisy signal, compromising measurement accuracy. loop, it can act as a secondary and complementary measurement
DAS is also limited due to the broad absorption line shape, with to the oxygen measurement, assisting LEA optimization and
measurement data contained within wings of the absorption introducing a further level of process safety-related diagnostics.
curve; hence a proportion of the absorption data is not scanned CO measurement using TDL also avoids the problem of high
and cross-interferences from background gases and environmental sulfur levels inhibiting catalytic sensors, while the ability to use
fluctuations are difficult to correct. While the disadvantages of compressed air as a purge gas removes the prohibitive costs associ-
the DAS technique is generally not significant in relation to O2 ated with using TDL for an O2 measurement. But as TDL offers
analysis, for all other gases it is limited to measurement accuracy. an average path measurement, rather than a point measurement, a
WMS is a sophisticated evolution of the DAS technique, catalytic measurement of CO combined within the same analyzer
which takes a measurement of the second harmonic of the as the zirconia O2 measurement gives greater diagnostic capabili-
absorption curve, to determine the rate of change in the absorp- ties for burner efficiency.
tion line shape. This yields a very sharp absorption curve with Possibly the most significant application for TDL in fired-
all measurement data contained within the laser scan width, and heater processes lies in the ability to integrate the technology into
very defined turning points which are easily computed, allowing flameout protection, specifically the measurement of methane in
an accurate evaluation of the area under the absorption curve. natural-gas burners. If TDL is installed so that a burner flameout
By delivering excellent cross interference rejection, precise tem- can be detected quickly, it enables greater flexibility and response
perature and pressure correction and low noise measurements, to control and shut down processes. In normal operating condi-
the greater accuracy and stability given by the WMS measure- tions, no CO or methane should be present in the process, so mois-
ment means it is consequently the most commonly used TDL ture analysis using the same TDL is used as a reference peak in the
measurement technique. same laser scan cycle to prevent laser drift and loss of laser line lock.
TDL-based systems appear an ideal choice for in-situ cross-stack
measurements in process and combustion control applications. Conclusion. In conclusion, zirconia and TDL technologies
As there is no physical or mechanical interaction with the pro- offer the process engineer the greatest advantage when considered
cess—other than molecular absorption—they offer a highly stable as complementary techniques to control the combustion process,
base-line measurement, with a long interval between calibrations reduce emissions and improve safety in fired heaters. As a general
and a fast response measurement in hot, wet and dusty process rule, the use of close-coupled extractive zirconia instruments to
conditions. TDL technologies therefore appear highly attractive on measure oxygen offers a point measurement that can be related
both cost and performance grounds, but the technology has poten- to specific burners and higher levels of inherent accuracy, coupled
tial disadvantages when compared to zirconia for a measurement. with true calibration capability. TDL offers a highly robust, aver-
For O2 analysis, TDL can only offer an average path measure- age and faster measurement, with less associated maintenance
ment across all burners, while zirconia analyzers can be used to which is ideal for monitoring purposes.
measure a particular section of burners by their ability to sample While TDL will continue to improve, it is not yet ready to
a single point. TDL is also susceptible to a range of environmen- displace the older technologies of zirconia and catalytic sensors
tal factors that must be compensated for, including path length within combustion control. Within the short to medium term, it
variation, window purge gas effects, optical interferences, and seems more likely that its introduction will trigger a new genera-
temperature and pressure changes. For a WMS instrument an tion of zirconia and catalytic sensor improvements and analyzer
error of approximately +/– 5% of reading is normal, while, for a developments. This competition between technologies will ulti-
DAS measurement, the error can be considerably higher. mately benefit process engineers and operators, as it will help
There is also no way of accurately calibrating a measurement generate new, cost-effective and reliable instrument solutions. HP
without removing both the TDL source and detector and fitting a
fixed-length calibration cell. Even with the calibration cell fitted,
which is usually one meter in length, a true calibration is difficult Rhys Jenkins graduated from Manchester University in 1994
with a BEng in mechanical engineering and joined Servomex in
to achieve accurately, as process path lengths typically vary from 1995 as a mechanical design engineer within a simultaneous-engi-
5-m to 20-m long. The instrument must apply correction factors neering team. Mr. Jenkins has worked extensively across Servomex’s
to compensate for the calibration cell path length and process path range of world-leading gas analyzers, being involved in a range of
length differences. key projects including development of the Fluegas 2700 combustion analyzer, the
digital range of SBSW infrared sensors, Servomex’s 5000 architectural platform and
Problems can also arise in the fitting of optical windows the 1900 range of infrared and paramagnetic oxygen portable analyzers. He is now
between both the source and the process and between the detec- the project manager for Servomex has been most recently instrumental in developing
tor and the process. These windows must remain clean at all times the award-winning SERVOTOUGH Oxy hazardous area paramagnetic gas analyzer.
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I FEBRUARY 2011 HydrocarbonProcessing.com
CALL FOR ABSTRACTS
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considered for the proceedings. This two-day conference, co-organized by the China National Petroleum Corporation,
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Topics to be covered include (but are not limited to):

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 PLANT SAFETY

Circumvent design issues when

adding new hydrotreating units
Follow these guidelines for substantial capital cost savings
with existing flare systems
M. H. MARCHETTI, A-Evangelista, S.A., Buenos Aires, Argentina

D
ue to higher global demand for gasoil a column with a cooling failure, power fail- ance (V1), the relief load is calculated as
and gasoline along with strict envi- ure or reflux failure, the energy balance is: L = 2,923 kg/hr.
ronmental regulations, refineries are • As an approximation, using (Q1 +
F  hF + QR = B  hB + P  hP + V  hV +
incorporating new hydrotreating units into QA)/reboiler, the relief load is L = 3,035kg/hr.
QA + Q1 + L  hL (1)
their existing facilities. Just in the southern Once the preliminary relief loads are
cone of Latin America (Argentina, Chile where: calculated, the new pressure-relief valves
and Uruguay) at least five hydrotreating F = Feed flow are sized, and the new flare system lines
units have been projected and/or built in hF = Feed enthalpy are designed and routed into a new unit
the last five years. These hydrotreating units QR = Reboiler duty subheader. While calculating the concur-
aim to lower the sulfur content to 20 ppm– B = Bottom liquid flow rent PSV contingency loads, most coming
50 ppm on final products. hB = Bottom liquid enthalpy from columns, towers or pressure separa-
Project attention focuses on these new P = Product flow tors, other process engineers can work on
hydrotreating units, while utilities and hP = Product enthalpy calculating all the single-contingency PSV
other services are evaluated later in the V = Vapor flow loads, such as blocked outlet loads, control
project cycle. Verifying the existing refinery hV = Vapor enthalpy valve full-open cases, etc.
flare systems has to be performed as early L = Relief load
as possible during the detail engineering hL = Relief load enthalpy HAZOP analyses and relief sce-
project phase to answer key questions, such QA = Air cooler (condenser) duty narios. A hazardous operation (HAZOP)
as: Would the existing crude distillation Q1 = Trim cooler (condenser) duty analysis of the new process enables assess-
unit pressure-relief valve (PSV) open with reboiler = Latent heat of vaporization or, ment of the number of PSVs that might
the new backpressure introduced from the for multicomponent systems, the differ- be triggered to open in various scenarios.
new hydrotreating unit’s PSV? Is the exist- ence between the vapor and liquid specific In a new gasoline hydrotreating unit, the
ing flare tall enough that it doesn’t exceed enthalpies. number of PSVs involved in a multivalve
the radiation limits at ground level? Are the The reboiler duty is recalculated for opening contingency, other than fire, that
emission contaminants changing compared relieving conditions. For an air-cooler con- could impact the existing flare design rating
to the previous refinery operations? tingency (or power loss), QA in relieving are shown in Table 1.
conditions would be 20% of operating QA. Out of 30 PSVs, only two were involved
Method description and best For cooling water loss, Q1 would be 0. To in concurrent PSV discharge scenarios—a
practice tips. The proposed method- evaluate a reflux failure, the top tray vapor cooling water and general power failure—
ology is used as a multi-tier approach to less the operating vapor to the condenser is
compress project schedules, determine a good approximation to calculate L.1–4,7 L
V1 V
PSV requirements earlier in the project
and purchase those PSVs early, if it’s eco- Example. With a new gasoline stabilizer QA CW Q1

nomical; assess alternatives to improve column without an air-cooler condenser P

design and save on capital costs without (QA = 0), the following quick calculations
compromising safety. were considered to estimate the relief load B
To quickly identify possible problems, for a loss of cooling in the condenser:
relief loads are first calculated using a • A steady-state simulation model was QR
simple approach. The different concurrent used (Fig. 2), setting the column pressure as
B
contingency loads can be calculated with the opening valve pressure and Q1 = 0. The
the basic material and energy balance engi- relief load is calculated as L = 3,732 kg/hr.
neering data. A conservative enthalpy bal- • For normal vapor flow to the con- FIG. 1 Material and energy balance in a
ance approach can be used. For example, in denser from the material and energy bal- column.
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HYDROCARBON PROCESSING FEBRUARY 2011
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PLANT SAFETY

Engineering workflow and guide-

lines. Fig. 3 represents the workflow of
the flare-system rating method. The vari-
ous steps are described as follows:
• Workflow starts with a parallel evalu-
ation of multiple PSV load contingencies
and single or unit-wide contingencies,
using a flare-system analyzer model.
• New flare network is designed. At this
stage in the detailed engineering project,
the new units’ isometrics are not available.
To complete the flare header design and
rating, basic routing of PSV exits are made
over the plot plan of the plant or layout of
new and existing units. Choosing the tie-in
point and knockout drum verification will
be discussed in detail later.
• The network is designed and rated to
project-specific values of ␳·v2 and Mach
FIG. 2 A steady-state simulation model. number. Good engineering practice uses
␳·v2 for gases of less than 150,000 Pa
and Mach numbers of 0.3 to 0.7. If these
parameters are not met in the existing main
Single-contingency loads Multiple-PSV load scenarios header, then a better understanding of the
existing relief loads can be achieved through
dynamic simulation. Once the hydraulic
calculations comply with the design param-
Design new flare PSVs, depressurization valves, eters, the PSV orifice calculations for the
exit lines, sub headers and headers (ISBL) multi-PSV opening cases are reviewed. Dis-
persion and radiation studies are performed
Verify knockout drum (KOD) with new vapor and liquid loads and, if all studies comply with international
Perform dynamic and local regulations, the flare-system rat-
simulation of columns,
or HIPPS analysis ing is completed.
Unfortunately, flare-system analysis
Add new KOD tie-in Tie-in point upstream does not always follow a straight path.
downstream existing KOD existing KOD, check
Mach. number Sometimes a more detailed analysis and
additional problem-solving solutions are
required, and these will be discussed further.
Verify ␳zv 2 and Mach number on existing header
downstream the tie-in point Tie-in point and final disposal
design. The tie-in location choice is gen-
erally made as close to the flare stack as pos-
Review PSV orifice calculation with calculated back pressure
sible, taking into consideration whether the
existing knockout drum can handle the worst
Perform dispersion and radiation studies case vapor and liquid loads. When a PSV has
a high setpoint and the volumetric flow for
the design case is high, the Mach number at
FIG. 3 Flare system rating method workflow. the tie-in point tends to be high as well. In
these cases, having a higher backpressure at
the tie-in point can reduce the Mach num-
TABLE 1. Gasoline hydrotreating unit relief scenarios ber. For example, moving the tie-in point
Contingency Fire Concurrent other than fire Single contingency only upstream in the existing flare header helps
Number of PSVs involved 25 2 4
reduce the Mach number; the consequence
is a slight increase in the backpressure.
and these potentially affect the existing flare dispersion was reduced to two. Only these Fig. 4 illustrates an example of a flare
header performance. All other contingen- two scenarios had to be studied further at a system analyzer simulation with a stabilizer
cies, including fire, were unit-wide sce- plant-wide level. All other new-unit scenar- PSV that has a high set pressure with its
narios but not plant- or refinery-wide sce- ios were studied separately to size the new tie-in point in the unit’s 16 in. subheader
narios. The number of plant-wide scenarios unit main header, which in this example and in a 30-in. main header. The 30-in. tie-
that might affect existing flare backpres- was determined to be governed by one of in point resulted in high Mach numbers
sure, radiation intensity and contaminant the fire cases. while the resulting Mach numbers using the
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86
I FEBRUARY 2011 HydrocarbonProcessing.com
 PLANT SAFETY

16 in. subheader were lower without exces-

sively elevating the PSV’s exit backpressure. Quemador 601-L
The resulting hydraulic performance for
both situations is shown in Fig. 4. 601-L
1101-16-in. C 100-RV-0001-30-in. A 1.11894/1.10724
The existing knock-out drum rating Nodo 5 Nodo 6 16 in. x 30 ft 0.109/0.110
can be performed in parallel with the flare-
header rating and later checked by the final 1101-16-in.–B Nodo 7 100-RV-0001-
simulation model. The various flare-header 30-in. AB2A
1.13374/1.12803
scenarios are loaded into the simulation 0.108/0.108
tool, and the PSV sizing and flare calcula- 610-F
tions are performed. The flare-tip pressure 1311-2-in. Tie-in 30-in. header
3400-RV-1122-14-AB2A
drop can be simulated, using the old design 2.03759/1.36906 mach 0.8
0.445/0.808 PSV BP = 2.03 bara
data and extrapolated to new loads, using a
Bernoulli Equation approximation: PSV-34026/27 PSV-34022
14.00500/ 11.53.000/2.03759
v ×ρ
2
0.445
+ P + ρ × g ×z = K
2 1101-16-in.–D
The process engineer can consider the 1.31911/1.22139
1101-16-in. C 0.360/0.394
backpressure problems that might arise Nodo 5 Nodo 6 16-in. x 30 ft
from these calculations on existing PSVs,
especially on the crude unit PSVs that have 1101-16-in.–B Nodo 7 100-RV-0001-
low pressure settings. For the new units, 30-in. AB2A
1.13373/1.12802
the project team can select the PSV types, 0.108/0.108
conventional or balanced, and purchase
these early if there are cost savings. 1311-2-in. 3400-RV-1122-14-AB2A
2.09626/1.58825 Tie-in 16-in. sub-header
The radiation intensity methods 0.430/0.624 Mach 0.6
described in API 521, a simple radiation PSV BP=2.09 bara
PSV-34026/27 PSV-34022
method, and Brzustowski and Sommer, can 14.00500/ 11.53.000/2.9626
be used to determine the radiation intensity 0.445
based on the worst case heat of combustion FIG. 4 Tie-in point diagram.10
calculations.1 Finally, the contaminant dis-
persion into the atmosphere can be calcu-
lated using the US EPA Screen 3 models.9 TABLE 2. Gasoline hydrotreating unit PSV changes between revisions
When to use dynamic simulation Rev. A Rev. 0
Project’s Month 5 Project’s Month 11
and relief considerations. The relief
Number of PSVs API orifice Number of PSVs API orifice
load calculation is a difficult task when rat-
12 D 13 D
ing or designing a flare system. The API
521 standard gives general guidelines on 0 E 2 E
estimating relief loads but leaves the cal- 2 F 0 F
culation details to the process engineer’s 3 G 3 G
judgment. 1 This is due to the different 1 H 1 H
approaches a process engineer can take to 1 K 1 K
perform relief-load calculations.
1 P 0 P
As previously discussed, typical scenar-
ios to consider for a column are related to 1 Q 0 Q
reflux, cooling or power loss. A dynamic 0 R 2 R
modeling approach has been used and doc- Total 21 22
umented, and it helped the engineers gain
additional insight on what happened during resulting in a relief load of L = 2,200 Kg/ drop does not increase substantially, and
a relief event.5 Often, this confirms that tra- hr. This load represented a 24% reduction there are no radiation or dispersion problems,
ditional methods are conservative, allowing of the lowest load estimation using steady then dynamic calculations can be avoided.
engineers to use reduced relief loads while state calculations.
still focusing on safety. However, dynamic One way to decide when to use dynamic Guidelines for hydrotreating
simulation takes time and tight project simulation and when to apply the standard unit flare analysis. Specifically for
schedules may make it difficult to use this steady-state calculations is to analyze if the hydrotreating units, the guidelines to rate
approach. Dynamic simulation benefits are contingency being studied impacts the whole and design a flare system comprise the fol-
clear and project teams are encouraged to flare system, involving multiple units across lowing load calculations and possible solu-
consider it when the situation requires it. the plant or refinery. If this contingency is tions, including dynamic simulation, to
A dynamic simulation (Fig. 5) was limited to a single unit and does not impact problems that may be encountered. These
performed for the new gasoline stabilizer, the whole flare system, and if the pressure guidelines include the usual analysis of
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HYDROCARBON PROCESSING FEBRUARY 2011
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PLANT SAFETY

defined by the World Health Organization

and other local regulatory authorities.

New sweet-loads evaluation:

Hydrotreating unit reactors usually work
at high temperatures and when the system
is evaluated at opening pressure for a fire
relief, the hydrocarbon/H2 mixture usu-
ally enters in a critical flow regime. In these
cases API 521 recommends using depres-
suring systems and dry fire calculations.
The loads calculated using API dry formu-
las are very conservative. A more accurate
approach is presented by Ouderkirk.8
The new flare-header design for
hydrotreating units is often governed by
one of these cases:
• Depressurization loads
• Fire loads
FIG. 5 Dynamic relief load calculations using a simulation model. • Electrical failure loads (considering
that most condensers are air coolers and
relief loads for cooling-water failure is mini-
TABLE 3. Gasoil hydrotreating unit PSV changes between revisions mal compared to an electrical failure).
If the multiple concurrent PSV design
Rev. A Rev. 0
Project’s Month 5 Project’s Month 11 scenarios do not comply with the conserva-
Number of PSVs API orifice Number of PSVs API orifice tive API 521 radiation limits or environ-
9 D 7 D mental regulations, it is worth calculating
the relief loads using dynamic simulation.
3 E 4 E
Most column relief loads can be calcu-
3 F 4 F
lated with a more rigorous model, and the
4 G 4 G revised loads are used to rate the overall
4 H 4 H flare system including recalculating the
1 J 1 J flare main header, the radiation intensity
0 K 0 K and the dispersion levels.
1 M 1 M
While the rigorous models are being
developed, the piping engineers might have
0 P 0 P
also completed the isometrics using the first
0 Q 0 Q non-rigorous simulation diameters. By the
0 R 0 R time the more rigorous load calculations
Total 25 25 are being done, these final flare simulations
can be performed, putting all the pieces
relief loads, but also additional consider- type, then it is advisable to perform a of the puzzle together (isometrics, revised
ation of new acid loads, etc. dynamic analysis of the PSVs that partici- multiple-contingencey loads, existing PSV
pate in that design contingency. This would pressures, etc.). This provides the most
Evaluate existing loads. Determine typically involve PSVs with greater volu- complete, accurate and rigorous analysis.
if, for a plant-wide concurrent contingency metric loads and usually concurrent scenar- If radiation intensity, back pressure or
(cooling or power loss, etc.), the new relief ios involving topping columns, absorbers, contaminant dispersion issues cannot be
loads added to existing loads resulted in stabilizers and FCC’s safety valves. resolved using the methodology presented,
any of the following effects or conditions other alternatives may be considered:
being violated: New acid loads. The new hydrotreating 1. Perform a high-integrity pressure
• Substantial backpressure changes on units concentrate H2S in the top vapor protection system (HIPPS) project to iden-
existing PSVs streams of unit operations. Most of the H2S tify which units control the relief loads,
• Radiation intensity at ground level is extracted in an amine contactor and then and perform a permutation analysis of the
corresponding to API 521 radiation limits sent to the amine and sour-water unit strip- individual relief loads by their probability
• Air contaminant dispersion comply- pers, which then have the flare loads rich in of occurrence and determine the applicable
ing with EPA and local environmental H2S and NH3. If the refinery doesn’t already safety integrity level (SIL). SIL is a measure
regulations. have a sour-flare system, then the company of the reliability of a safety instrumented
If any of the verification steps fail, the should consider building one when add- system to function as designed. There are
solution is to change the existing conven- ing the new hydrotreating unit. Dispersion three possible discrete integrity levels (SIL
tional PSVs to a balanced (bellow or pilot) constraints are key in designing this system 1, SIL 2 and SIL 3) of safety instrumented
type. If the existing PSVs are a balanced with concentration limits for SO2 that are systems defined in terms of probability of
KPE
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I FEBRUARY 2011 HydrocarbonProcessing.com
 PLANT SAFETY

3
failure on demand (PFD). SIL 3 has the approach presented in this article, as vali- K. Banjee, N. P. Cheremisinoff and P. N.
highest reliability, SIL1 has the lowest. API dated by experience on several projects: Cheremisinoff, Flare Gas Systems Pocket
Handbook, Gulf Publishing Company, 1985.
521 Fifth Edition allows you to take load • Compressed project schedules by per- 4 Kister, H. Z., “Distillation Operation,”
credits for the use of HIPPS.1 The benefit forming PSV calculations and flare system MacGraw-Hill, Inc, Chapter 9.
5 Gruber, D., D.-U. Leipnitz, P. Seturaman,
of this approach is the avoidance of having calculations in parallel. For the example
to build a complete new flare. The down- cited previously, these calculations resulted M. Alos, J. M. Nougues and M. Brodcorb,
“Are there alternatives to an expensive overhaul of
side is the operational constraints on the in achieving a three-month reduction in the a bottlenecked flare system?, Petroleum Technology
degree of turndown or the possibility even project schedule. Quarterly, Q1 2010.
6 Marshall, B., “Improve Flare System Design
having to shutdown a unit to avoid over- • Project man-hour savings by perform-
loading the flare system, and the capital ing the appropriate level of modeling as to Reduce Cost and Enhance Safety,” AspenTech
Webinar, November 2009.
investment needed to enhance the control required by the project-specific design. The 7 Crosby, T. Pressure Relief Valve Engineering
systems of existing units. example cited represented saving 160 engi- Handbook, Technical Document, May 1997.
8 Ouderkirk, R., “Rigorously Size Relief Valves
2. Increase existing flare height. The neering man-hours of modeling time.
radiation intensity and dispersion con- • Early definition of header sizing and for Supercritical Fluids,” CEP Magazine, August
2002.
centration at ground level will improve the PSVs required. There may be cost sav- 9 US Environmental Protection Agency, “Guía
but the support structures may have to be ings in procuring these supplies early. del usuario del Modelo SCREEN3,” EPA454/
revamped or new structures added. • Material capital cost savings in accu- B95-004, September 2000.
10 Simulation performed with Aspen Flare System
3. Change the existing main flare rate header sizing.
Analyzer V7.1, Aspen Technology, 2009.
header. Sometimes backpressure prob- • New flare cost savings in performing
lems persist in existing PSVs and the only more accurate dynamic-load calculations
option is to replace portions of the existing when needed. HP
network. Obviously, this will require addi- Mayra Marchetti is a process
LITERATURE CITED engineer at A. Evangelista S.A. She has
tional capital investment. 1 ANSI/API Standard 521 (ISO 23251), “Pressure- 10 years´ work experience in process
4. Add a gas-recovery facility. When relieving and Depressuring Systems,” Fifth simulation and industrial projects, with
a dispersion analysis results in high con- Edition, January 2007. a special focus in relief system design
2
taminant concentration, this approach ANSI/API Standard 520, “Sizing, Selection and evaluation studies, revamps and new designs. She
could partially solve the problem, but it and Installation of Pressure-Relieving Devices graduated as a chemical engineer from Buenos Aires
in Refineries. Part I: Sizing and Selection,” Seventh University and holds an MS degree in engineering man-
also might increase the backpressure on the Edition, January 2000. agement from Florida International University.
PSVs and increase capital cost.
5. Change the flare tip. Sometimes,
high Mach numbers at the flare tip can be
avoided by simply changing the flare tip.

Results obtained by applying

CUSTOM
this method. The results of applying
this approach to flare-system analysis in a
project involving the addition of two new
hydrotreating units to an existing refinery
are discussed below.
Tables 2 and 3 show the number of
REPRINTS
PSVs that changed from one type to a dif- REPRINTS ARE IDEAL FOR:
ferent type as the project progressed. This
Q Product announcements
resulted from the simulation model being
improved as various engineering tasks Q Sales aid for your field force
were completed, and as the overall design Q PR materials and media kits
evolved and improved. Q Direct mail enclosures
Even though many load calculations
changed and PSV sizes were revised during Q Trade shows
the project, the unit’s main header diame- Q Conferences
ter, the tie-in point and the knockout-drum
calculations remained unchanged between
design revisions.
This experience demonstrates that some
tasks can be performed in parallel. Later
in the project cycle all pieces of the flare For additional information, please contact
system can be quickly recalculated using Foster Printing Service, the official reprint
process simulator and flare system analysis provider for Hydrocarbon Processing.
software.
Call 866-879-9144
Benefits of using this method. or [email protected]
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Company Page RS# Company Page RS# Company Page RS#
Website Website Website

ACS Industries Inc. . . . . . . . . . . . 67 (166) Gulf Publishing Company NPRA . . . . . . . . . . . . . . . . . . . . . 78 (90)

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 HPIN CONTROL
Y. ZAK FRIEDMAN, CONTRIBUTING EDITOR

[email protected]

Inferential control model input selection

It is not a secret that I prefer to base inferential models on engi-
neering principles, rather than on regression. Having said that, the
use of regression is widespread, and being a consultant in the field, PI LC PC
I am often asked about how inferential model performance can be TC
improved. Indeed it can be much improved, if one only took the FC FC
Naphtha
trouble to consider chemical engineering principles.
TI
Example. A classic example of bad input selection is a set of FC
Pumparound
input variables that contain intensive variables, such as pressures Pumpdown
and temperatures, together with extensive variables such as flows. FC
The fluid catalytic cracking (FCC) fractionator (Fig. 1) will serve TI LC FC
TI LCO
to illustrate this point. To infer the naphtha 90% point regression
practitioners habitually take these regression model inputs:
1. Column top temperature Reactor effluent
PI
2. Column top pressure
3. Naphtha product flow. LC FC
Why naphtha product flow? How can such a blatant violation
of process engineering facilitate a successful inference? Answer: There
is a correlation of flow against 90% point because at a fixed through- FIG. 1 Classic example of bad input selection—FCC fractionator
put and severity, increasing the naphtha yield increases the naphtha with total draw trays.
cutpoint. That following a throughput change the inference would
be erroneous is just one example of inferences that correlate but do 1. LCO draw temperature
not predict. Such inferences fail during a transient operation, when 2. Column top pressure
they are needed the most. Can this problem be solved by inputting 3. LCO product flow.
naphtha yield instead of naphtha flow? It is definitely an improve- Why LCO flow? Again, for the same reason, at steady opera-
ment but still vulnerable to reactor severity or feed quality change. tion, increasing LCO yield affects the LCO cutpoint. Of course,
Why is there a need for naphtha flow or yield input to begin such an inference is again weak. It can handle neither throughput
with? Process engineering dictates that the naphtha 90% point is nor severity changes. And for the side draw, there is another ele-
a function of column top partial pressure and temperature, with ment of uncertainty. LCO yield can be changed in different ways.
some internal reflux influence on the heavy distillation tail. It takes For example, at steady operation, if naphtha yield changes up and
some engineering calculations to create a partial pressure input, LCO yield down, then the LCO 90% point would actually not
and regression practitioners have become “purists” in the sense that move at all. The LCO inference is vulnerable not only to transient
they would not consider any engineering procedure—only straight throughput and severity but also to normal manipulation of the
measurements. Because total pressure is an imprecise input, the use fractionator top section.
of naphtha yield or flow “improves the fit.” I do not recall seeing a Internal reflux in the LCO section affects both the partial
calculated partial pressure anywhere as a regression inferential input. pressure and heavy distillation tail. Is it possible to take that into
FCC reactors have several significant steam injections, all of account? The fraction (Fig. 1) has a total draw LCO tray where
which end up in the fractionator. Reactor steam injections are internal reflux is measured as pump down, so even the purist
determined by reactor considerations and are not necessarily statistician should accept that.
proportional to the feed. Inputting total pressure in lieu of partial Process engineers spend years studying chemical engineering,
pressure is not a very good idea. Further, the FCC reaction creates then more years performing process calculations on the real plant.
a large amount of LPG and gas. At fractionator top conditions, Where is all that accumulated knowledge? Please, show the world
those light components are not miscible and, in terms of their that a process control engineer is not a statistician. HP
effect on partial pressure, they behave like steam. I would assert
The author
The author isis aa principal
principal consultant
consultant in
in advanced
advanced process
process control
control and
and online
online
that no reasonable inference can be created without partial pres- optimization with
with Petrocontrol.
Petrocontrol. He
He specializes
specializes in
in the
the use
use of
of first-principles
first-principles models
models
optimization
sure being one of the inferential inputs. for inferential
for inferential process
process control
control and
and has
has developed
developed aa number
number ofof distillation
distillation and
and reactor
reactor
models. Dr.
models. Dr. Friedman’s
Friedman’s experience
experience spans
spans over
over 30
30 years
years in
in the
the hydrocarbon
hydrocarbon industry,
industry,
Things go downhill from here. What would you suggest working with
working with Exxon
Exxon Research
Research and
and Engineering,
Engineering, KBC
KBCAdvanced
AdvancedTechnology
Technologyand, and since
since
1992 with
1992 with Petrocontrol.
Petrocontrol. He
He holds
holds aa BS
BS degree
degree from
from the
the Israel
Israel Institute
Institute ofof Technology
Technology
as inputs for inferring light cycle oil (LCO) 90% point? The (Technion) and
and aa PhD
PhD from
degree from Purdue University.
(Technion) Purdue University.
regression practitioner would typically use:
KPE
94
I FEBRUARY 2011 HydrocarbonProcessing.com
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