TECHNOLOGIES FOR CLEAN AND

RENEWABLE ENERGY PRODUCTION

RESIDUE UPGRADATION 2
DR. PRASENJIT MONDAL
CHEMICAL ENGINEERING DEPARTMENT

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 Contents

Petroleum Residue and its upgradation

Residue upgradation routes
SDA
Visbreaking
Delayed coking
Gasification

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 Visbreaking
 Visbreaking, an abbreviated term of viscosity breaking, is a mild predominantly
liquid phase thermal cracking process, where high molecular weight
hydrocarbons are broken thermally into lower molecular weight ones, yielding
products of low viscosity and low pour point.
 Petroleum residue is converted to small amount of light hydrocarbons such as
LPG, naphtha, gasoline etc., heavy gas oil and residual part with reduced viscosity
 It has been developed to produce fuel oil resulting in saving the valuable lighter
products called ‘cutter stocks’. It is also used to prepare feed stocks for secondary
units like FCC and Hydro Cracker.
 The mild operating conditions are essential because
 Feedstocks are heavy and more susceptible to cracking
 Allowable conversion to gasoline is lower in visbreaking due to fuel oil
stability requirements
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 Visbreaking mechanism
 It is a complex process and the reaction mechanism for the production of light
hydrocarbon can be expressed through a typical free radical mechanism (Eq. 1 to 10):
Initiation
C6H14 C2H5• + C4H9• (1)
(i) (ii)
Propagation
C2H5• + C6H14 C2H6 + C6H13• (2)

C4H9• + C6H14 C4H10 + C6H13• (3)

Radical (ii) can be cracked to different species as per Eq. 4 to 6,as big radicals are
unstable and decompose to form olefins and smaller radicals.
C4H9• C4H8 + H• (4)
C4H9• C3H6 + CH3• (5)
C4H9• C2H4 + C2H5• (6)
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 Visbreaking mechanism
Radical C6H13• may further be cracked as per Eq. 7:

C6H13• C4H8 + C2H5• + Many other products (7)

Termination

The free radical chain reaction is terminated when the radicals combine:

C2H5• + H• C2H6 (8)

C2H5• + CH3• C3H8 (9)
CH3• + H• CH4 (10)

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Visbreaking : Process flow sheet A typical visbreaking unit consists of a furnace reactor, a flash
chamber and a fractionating column

Furnace

• The furnace is normally coil type

• Furnace inlet temperature 305-3250C and pressure 15-40 bar
• Furnace outlet temperature 480-5000C and pressure 2-10 bar
• Residence Time 2- 5 minutes
• Steam injection 1 % Volume
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 Visbreaking : Process
 To reduce the furnace temperature a soaker unit is placed between flash chamber and
furnace.
 Temperature and pressure maintained at soaker unit are 440-4600C and 5-15 bar with 20-
30 minutes residence time respectively.
 Preheating of the feedstock to ~ 335oC is done by using visbreaking tar.
 The overhead product of the flash chamber gives naphtha, LPG, gasoline etc., and the
bottom liquid is further fractionated into gas oil and residual product (reduced viscosity).
 Through this process around five-fold viscosity reduction is possible when 5-10 % naphtha
is produced.
 Depending upon the reactor design this process can be classified into two categories i.e,
soaker visbreaking and coil visbreaking
 The soaker visbreaking process is a relatively low-temperature process with relatively high-
residence time (100-300 s for coil visbreaker and 1200-1800 s for soaker visbreaker).

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 Visbreaking : Process

 In soaker visbreaking two stage conversion, a minor degree of conversion for short period
in the furnace and the majority conversion in soaker unit for predetermined extended
period takes place. The low temperature operation saves fuel consumption, however,
decoking in soaker unit require more equipment and handling cost.

 Similarly the application of internals in soaker visbreaker is an important development,

which controls the back mixing in the soaker unit.
 Back mixing can enhance over cracking, which reduces stability of fuel oil and can be
avoided if radial gas phase hold up profile is flat.
 Application of soaker internals satisfies this condition and controls stability of products

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 Visbreaking : Process

Comparison of performance of internals in soaker unit (Kumar et al., 2004)

Soaker Soaker
(without internals) (with internals)
Temperature, 0C 420 420

Conversion (150 0C), wt% 2.90 4.12

Kin Vis, cSt at 100 0C (1500C+ 248.43 230.67

Residue)
Stability (150 0C+ Residue) Stable Stable

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 Delayed coking
• A severe thermal cracking process
• Aimed at upgradation of petroleum residue by converting it to liquid and gas
products
• Coke is left behind as a solid concentrated carbonaceous material
• Term “Delayed” refers to delayed reaction which initiates in coil furnace, but
completes in coke drum by “delaying” the process
• Predominant coking technology
• Relatively inexpensive
– Considering open art
– Companies do license technology emphasizing coke furnace, special processing
modes and operations.

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 Delayed coking: Reactions and Mechanism
 Generally, two types of reactions take place
 Primary Reactions
 Decomposition of large molecules to smaller molecules takes place
 Secondary Reactions
 Active products from primary cracking reactions further crack or react to
form other compounds, or polymerize to give heavy products
 Two types of mechanism are proposed for coke formation
 Mechanism 1
Very high molecular weight compounds such as asphaltene and resins tend to
dealkylate when subject to high temperatures. The peptizing phase also cracks and
colloidal suspension is distorted resulting in the precipitation of high mol. wt.
compounds to form a high cross linked structure of amorphous coke

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 Delayed coking: Reactions and Mechanism
Mechanism II
It involves the polymerization and condemnation of aromatics, grouping a large
number of these compounds to such a degree that eventually coke formation takes
place. The coke produced in this manner contains fewer cross linkages and has a
more crystalline appearance than the resin asphaltene type of coke
 Due to its amorphous nature and high impurities concentration, the coke
produced from the resin asphaltene compounds is very undesirable for
manufacturing high grade carbon anode
 Coke formed from feedstock containing a high concentration of aromatics and
low concentration of resin asphaltene compounds gives a premium grade carbon
anode after calcining and graphitization. This type of coke is called needle coke.
This term applies because the particles appear as needle rather than as sponge.
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 Delayed coking: feedstock and products
• Typical feedstock – Vacuum Residue (Atm. Residue occasionally used)
• Typical Feed composition
– 6 % Sulfur
– 1,000 ppm (wt) metals
– CCR of 20 – 30 wt.%
• Feed ultimately depends on the type of coke desired

Products
Gas : Coker gas; C3, C4 is recovered as LPG and the lighter end can be used as fuel gas

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Liquid: Delayed coking: feedstock and products
Naphtha : Contains high olefin content and usually sent to the hydrotreating
units in the refinery for stabilization.
Heavy liquid products gas oil : Sent to the catalytic cracking units where the
valuable transportation fuels (gasoline, diesel and jet fuel) are produced.
Solid
The coke from delayed coking process can be simply characterized by the features
of coke’s outlook:

Sponge coke
Shot coke
Needle coke

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 Needle coke is a premium quality carbon used in the production of
high grade graphite electrodes for the application in electric arc steel
industry. Since these electrodes are subjected to rapid and large
extremes of temperature, a low CTE is one of the most important
Characteristics Values for needle
requirement of the needle coke
coke
Volatile matters, %wt < 0.50
 Needle coke properties depend upon:
Ash, % wt < 0.40
• Feed quality
Sulphur, % wt < 0.80
• Operating parameters
Real density, gm/ml > 2.10
 Needle coke specification
CTE(x 10-6/oC) < 1.25

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 Delayed coking: Process flowsheet
Modified from Gas
Sarvarkar et al. 2007 Cooling Reflux
water drum
http://repository.ias.a
Coke Coke c.in/39575/1/15_pub. Unsaturated
drum drum pdf naphtha
Fractio
nator Gas
oil
Steam
strip Steam
Heater per Gas oil

Coke Fresh feed

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 Operating variables
 Transfer/ Coke drum temperature
 Pressure in coke drum
 Recycle ratio (Composite feed/Primary feed)
 Reaction time
 Steam addition
• Coke yield decreases as drum temperature increases. If temperature is too low
coking reactions do not proceed further and form pitch or soft coke
• Very high temperature makes the coke removal difficult from the drum
• Temperature controls the volatile combustible matter content of the coke
products
• Decrease in coke drum pressure reduces coke yield. Each 0.5 kg/cm2 reduction
in drum pressure increases liquid yield by 1.3 % vol. and cut in coke yield by 1.0
% wt of fresh resid feed
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 Operating variables
• For making premium grade coke the coke drum pressure should be high. It
improves coke quality by CTE and electrical resistivity
• Increasing recycle ratio increases coke make and improves properties
• It lowers the combined feed resin asphaltene content and in turn provides a
higher concentration of aromatics in coke drum
• It also reduces coke deposition in coil
• Steam in the heater tubes prevents coke formation in the heater, which can
shut the unit down.
• It has a bad effect on the coke yield and quality as the stripping action that
steam has on the residual oil on the coke; remove oil from the coke
 Feed quality also influence the coke yield and quality
High density feed High C/H ratio high CCR high coke, less distillate
Coke yield α CCR
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 Delayed coking: drum cycle
Drum Cycle Hours
Steam to Fractionator 0.5
Steam to Blow down 0.5
Depressurize, Water quench and Fill 4.5
Drain 2.0
Unhead Top and Bottom 0.5
Cutting Coke 3.0
Rehead / Steam Test / Purge 1.0
Drum Warm-up (Vapor Heat) 4.0
Total Time 16.0

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 Coke Yields
• Coke and liquid yields may be estimated by simple equations as under
(http://www.jechura.com/ChEN409/)
Coke Yield ( wt % ) = 1.6 x (wt % CCR)
Gas (C4 - ) ( wt % ) = 7.8 + 0.144 x (wt % CCR)
Gasoline ( wt % ) = 11.29 + 0.343 x (wt % CCR)
Gas Oil ( wt % ) = 100 – (wt % Coke) – (wt % Gas) – (wt % Gasoline)
186.5
Gasoline(vol%)  x( wt%Gasoline)
131.5 API
0

155.5
GasOil( vol%)  x( wt%GasOil)
131.5 API
0

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 Gasification

• VR and pet coke can be used to produce syngas through

gasification
• Since petcoke is very hard and less reactive, requires high
temperature
• Entrained bed gasifier is more suitable for this feedstock
• IGCC concept will be more attractive

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 Some VR and pet-coke based gasification plants
Country Plant Name Technology Feedstock Products Syngas Year
cleaning
option
China Dalan Chemical Texaco Visbreaker residue Ammonia Rectisol 1995
Industrial Corp.
China Inner Mongolia Shell Vac. Residue Ammonia Rectisol 1996
Fertilizer Co.
China Juijang Shell Vac. Residue Ammonia Rectisol 1996
Petrochemical Co.
China Lanzhou Chemical Shell Vac. residue Ammonia Rectisol 1998
Industrial Co.

France Normandie IGCC Texaco Fuel oil Electricity, steam 2005

plant and H2
France - Texaco Refinery residue H2 Selexol 2006
USA Polk Country Texaco Pet coke Electricity 2005
gasification plant

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 Country Plant Name Technology Feedstock (4) Products Syngas Year
(1) (2) (3) (5) cleaning (6)
option
Germany Leuna methanol Shell Visbreaker H2, methanol 1985
Anlage residue and electricity
Germany Slurry/oil Lurgi MPG Oil and Slurry Electricity and 1968
gasification methanol
Holland Pernis refinery Shell Resid oil Electricity 1997
India Gujrat National Texaco Refinery Ammonia Rectisol 1982
Fertilizer Co. residue
India Bhatinda IGCC Texaco Pet coke Electricity 2005
Italy ISAB Energy Texaco ROSE Asphalt/ Electricity, H2 MDEA 2000
Project Heavy oil ,steam
Italy SARLUX GCC/H2 Texaco Visbreaker Electricity, H2 Selexol 2001
plant residue and steam
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 Country Plant Name Technology Feedstock (4) Products Syngas Year
(1) (2) (3) (5) cleaning (6)
option
Italy Agip IGCC Shell Visbreaker residue Electricity and H2 Amine 2003

Italy Sannazzaro GCC Texaco Visbreaker residue Electricity 2005

plant
Japan Marifu IGCC plant Texaco Pet coke Electricity 2004

Japan Nippon Pet. Ref. CO. Texaco Vac. Residue Electricity ADIP 2004

Japan Yokohama Cogen/ B Texaco Vac. Residue Electricity 2003

Netherlands Pernis Shell gasifier. Shell Visbreaker residue H2 and Electricity Rectisol 1997
Hydrogen plant

Poland Gdansk IGCC plant Texaco Visbreaker Electricity, H2 and 2005

residue steam

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 Country Plant Name Technology Feedstock (4) Products Syngas Year
(1) (2) (3) (5) cleaning (6)
option
China Dalan Chemical Texaco Visbreaker Ammonia Rectisol 1995
Industrial Corp. residue
China Inner Mongolia Shell Vac. Residue Ammonia Rectisol 1996
Fertilizer Co.
Portugal Quimigal Aducos Shell Vac. Residue Ammonia Rectisol
Singapore Chawan IGCC plant Texaco Residual oil Electricity H2, Flexorb 2001
steam
Singapore Singapore Syngas Texaco Visbreaker H2, CO (for acetic 2000
tar acid)
Spain Bilbao IGCC plant Texaco Vac. Residue Electricity and H2 2005

Spain PIEMSA Texaco Visbreaker tar Electricity and H2 MDEA 2006

USA Wabassh River E-GAS Pet coke Electricity MDEA 1995

Energy Ltd. (Destec/Dow)

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 Country Plant Name Technology Feedstock (4) Products Syngas Year
(1) (2) (3) (5) cleaning (6)
option
USA Coffeyville Refinery Texaco Pet. Coke H2, NH3 2000

USA Farmland Industries Texaco Pet. Coke Ammonia Selexol 2000

Lnc.
USA ExxonMobil Texaco Deasphalter H2, CO Rectisol 2001
Baytown Syngas bottom
project
USA Valero Refinery Texaco Pet. Coke Electricity, steam 2002

USA Port Arthur GCC E-GAS Pet coke Electricity 2005

Project
USA Lake Charles IGCC Texaco Pet coke Electricity, H2 and 2005
plant steam
USA Deer Park GCC plant Texaco Pet coke Electricity, syngas 2006
and steam
USA Polk Country Texaco Pet coke Electricity 2005
gasification plant

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Thanks

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