1

MTBE Units Expansion/Conversion

CDTECH
Introduction
Gasoline standards throughout the world are continuing to move toward cleaner
burning gasoline. This includes mandating limits on aromatics, benzene, sulfur,
RVP and distillation characteristics. All of these changes must be met while
maintaining or increasing gasoline octane. Some of the possible blendstocks that
fulfill the above requirements are isomerate, alkylate, oxygenates and iso-octane.
While isomerate offers some octane boost, it is substantially less than the boost
derived from alkylate, oygenates and iso-octane.
Conventional alkylation units all use sulfuric or hydrofluoric acid as catalyst, which
are highly corrosive and toxic, and would raise significant environmental concern.
In addition, alkylate is normally not a commercially available commodity but rather a
captive stream used in the refinery.
Methyl-Tert-Butyl-Ether (MTBE) became the single most widely used oxygenate in
RFG, primarily for its superior blending characteristics and economics compared to
ethanol, its main rival in the oxygenate market. However, concern was raised over
the wide use of MTBE, especially in California, where MTBE was detected in some
watrer wells. With pressure from the regulators to reduce or eliminate the use of
MTBE as a blending component in gasoline, refiners may be forced to use
alternative blendstocks.
Catalytic Distillation technology enhances production of MTBE. CDTECHs
CDMtbe

technology can be used for design of new units as well as expanding

existing units.
Iso-OctAne is the high octane C
8
product, rich in iso-octane, resulting from selective
dimerization of isobutene using CDTECH/Snamprogettis CDIsoether
SM
technology.
Page 2
Installation of a new CDIsoether unit or revamping an existing MTBE unit using
CDIsoether technology offers an economic solution to producing superior C
8
blendstock.
CDMtbe Technology
Prior to 1981 all MTBE was produced using conventional fixed bed reactors. The
reaction of isobutylene with methanol over a strong acid ion exchange catalyst
produces an equilibrium mixture of MTBE. The reaction is exothermic and
increasing temperature pushes equilibrium back towards the reactants, isobutylene
and methanol. Conventional technology utilizes two fixed bed reactors to
accomplish the reaction (Figure1).
The first bed is operated with a large recycle of cooled reactor effluent to limit the
reaction temperature rise by dilution. This step produces most of the conversion
(90%) and operates far enough from
equilibrium so that the reaction rate is
limited by kinetics rather than equilibrium.
The net effluent of the first reactor is
cooled and fed to the second reactor
without any diluent. Here, the reaction
proceeds at much lower rate at close to
equilibrium conditions. With the use of
excess methanol, a typical isobutylene
conversion of 96% is achieved. Recent
catalysts with higher activity have
achieved 97% conversion.
Figure 1 Conventional MTBE
Ether Produc
HC
Feed
Fresh Methanol Raffinate to
Methanol
Recovery
Primary
Reactor
Distillation
Column
Secondary
Reactor
Recycle
Pump
Recycle
Cooler
Page 3
The problem with fixed bed reactors is that the catalyst eventually loses activity and
conversion levels fall accordingly. The catalyst continually loses activity due to
thermal degradation but the major culprit is usually catalyst poison in the C4
feedstock. Some designs try to
delay the conversion loss with a
large excess of catalyst resulting in
very big reactors. Still the
conversion will fall and MTBE
production will suffer until the catalyst
is replaced. The improvement to
conventional technology is CDMtbe
(Figure 2).
A fixed bed reactor is still used for the bulk conversion of isobutylene, However the
version used by CDTECH is a boiling point reactor. It operates at lower pressure
so that when the heat of reaction heats the reaction mix up to the desired
temperature, the additional reaction heat is absorbed by partially vaporizing the
liquid mix. This method provides precise temperature control and does not waste
the heat of reaction by rejecting it to cooling water. A recycle stream and recycle
cooler are not required and the resulting reactor size is reduced since diluent is not
required for refinery FCC feedstocks. The two phase reactor product is discharged
to the fractionation column where the heat of reaction contributes to the heat load
required by the distillation.
The alternative to the conventional second fixed bed reactor is catalytic distillation
(CD). The catalyst is contained in CDModules
SM
which promote simultaneous
reaction and distillation. Due to its higher boiling point MTBE is easily separated
from the isobutylene and methanol. As a result the equilibrium reaction is shifted to
higher conversion. Higher reaction rates can be achieved because higher
temperature is possible at the reduced MTBE concentration. The heat of reaction
also contributes to the distillation heat load. A typical isobutylene overall
conversion of 98% is demonstrated on FCC feedstocks. As the catalyst in the
Figure 2 - Catalytic Distillation
Ether
Product
HC Feed
Fresh
Methanol
Raffinate to
Methanol
Recovery
Boiling
Point
Reactor
Catalytic Distillation Column
Page 4
boiling point reactor loses activity, the conversion of isobutylene is gradually moved
to the catalytic distillation column. High overall conversion has been demonstrated
continuously over the three year life of the CDModules (Figure 3). The difference in
net MTBE production over the three year period can be as much as 5.5%.
Figure 3 - More MTBE from CD
99
97
95
93
89
91
87
85
1 0 2 3
Conventional
Fixed Bed
CDMtbe
5.5 % Higher
Years
%

I
s
o
b
u
t
y
l
e
n
e

C
o
n
v
e
r
s
i
o
n
Addition of a catalytic distillation column is an economical means to increase the
capacity of an existing conventional MTBE unit. The two existing fixed bed reactors
can be arranged in parallel and a CD Column added to handle the effluent from
both reactors. In this arrangement, it is possible to essentially double the capacity
of the existing unit. The remaining equipment can be debottlenecked or parallel
equipment added to meet the desired capacity.
The CDIsoether
SM
Technology
Iso-octane (2,2,4-trimethyl-pentane) is the reference compound for the
measurement of octane and, by definition, has a clear RON and clear MON of 100.
Iso-OctAne refers to a product very rich in iso-octane (or similar tri-methyl-
Page 5
pentanes), produced by selective isobutylene dimerization followed by olefin
saturation using CDIsoether process. Although this dimerization technology has
been known since before World War II, Snamprogetti was the first company to
revise this reaction and to substantially improve selectivity to the desired dimer
products. The work, begun in 1994, was previously presented at NPRA Annual
Meetings
1,2
. In the second half of 2000, Catalytic Distillation Technologies
(CDTECH) and Snamprogetti agreed to combine and market their expertise in
isobutylene dimerization technologies. The features offered by the combined
technologies have allowed further optimization of capital cost, isobutylene
conversion and selectivity to high-octane gasoline blendstock for refinery,
petrochemical and chemical-based units. The combined technology, called
CDIsoether, provides the most flexible and cost-effective solution to revamp
existing MTBE plants to Iso-OctEne/Iso-OctAne production.
A typical flow scheme for the CDIsoether unit can be represented as follows:
Primary
Reactor
C
4
Raffinate
Feed
Wash
Catalytic
Distillation
C
4
Feed
Oxygenate
Recycle
Water
Waste Water
Iso-octane Olefin
Saturation
Unit
Isooctene
H
2
Feed
Off-gas
Figure 1: Flow Scheme
Page 6
Isobutylene is dimerized on an acid resin catalyst into a diisobutylenes-rich,
Isooctene fraction (Iso-OctEne product). Optionally, isobutylene can be partially
etherified into MTBE, or ETBE, and partially dimerized into Isooctene. The Iso-
OctEne product can be then hydrogenated into an iso-octane-rich alkylate (Iso-
OctAne product). The dimerization process can be used in any existing MTBE (or
ETBE) plant, irrespective of the C
4
stream source (FCC, isobutane
dehydrogenation, or steam cracking).
The CDIsoether technology uses an oxygenate selectivator, which moderates the
resin acidity to overcome some typical drawbacks of prior technologies, typically
arising from difficult temperature control. Without good temperature control,
excessive formation of heavier oligomers (trimers, tetramers) could occur resulting
in poor distillation characteristics of the product.
Different selectivators can be used to control the product quality. Tert-butyl-alcohol
(TBA) and Methyl-tert-butyl-ether (MTBE) are two well-studied components (water
or methanol will have the same effect since they equilibrate with TBA or MTBE). It
may be advantageous to use either selectivator depending on the specific
requirement. MTBE is more tuned to cases that require to have the flexibility to
produce either MTBE or Iso-OctEne, while TBA is more tailored for a market where
MTBE has been banned. In particular cases, a mixture of the two selectivators can
be used.
The main reaction in the Iso-OctEne synthesis is the dimerization of isobutylene to
2,4,4-trimethyl-1-pentene (DIB). Side reaction include co-dimer (trimethyl-
pentenes, dimethyl-hexenes) production as well as trimers (C
8
) and tetramers (C
12
)
due to isobutylene reacting with n-olefins and further oligomerization respectively.
In the olefin saturation unit, the C
8
and C
12
olefins are hydrogenated to respective
paraffins. The following Reactions represent the process chemistry in a TBA
selected CDIsoether process for the Iso-OctEne synthesis:
Page 7
Main Reaction:
Side Reactions:
or
Isobutene
CH
2
= C CH
3
CH
3
Isobutene
CH
2
= C CH
3
CH
3
+

CH
3
- C CH
2
C =
CH
3
CH
2
CH
3
CH
3
CH
3
C CH = C
CH
3
Iso-octene
CH
3
CH
3
CH
3
Isobutene + n-C
4
Codimer
Isobutene + Isooctene Tri-isobutylene
Isooctene + Isooctene Tetraisobutylene
(Trimers)
(Tetramer

sec-Butanol + C
8
Ether
Isobutene + Water TBA
n-butene + Water sec-Butanol

Page 8
Reactor Options
CDTECH and Snamprogetti bring their vast experience base in MTBE production,
and offer a variety of reactor systems in order to optimise revamping or grass root
construction:
Boiling point fixed-bed reactors (BPR): Temperature is controlled without
heat removing systems. Excellent option for existing MTBE unit with BPR;
lowest capital cost revamps.
Catalytic distillation towers (CD): Excellent finishing reactor to achieve high
selectivity and high isobutylene conversion without additional capital
investment.
Water-cooled tubular reactors (WCTR): Excellent temperature control,
especially for highly concentrated isobutylene C
4
feedstocks, as it gives very
high conversion per pass without requiring any recycle.
The proper combination of these different reactors allows achievement of various
conversion targets with high selectivity and without recycle. According to the
specific situation and the specific C
4
feedstock processed, an optimum solution can
be developed.
Hydrogenation is carried out in a typical trickle-bed reactor. Depending upon the
nature of the C
4
feedstock treated and the level of contaminants contained, different
hydrogenation catalysts can be employed: nickel-based for very clean feedstocks,
palladium based for low to medium content of contaminants or Ni-Mo catalysts for
highly contaminated feedstocks. Iso-OctAne product with very low olefin content (<
1%) can be achieved in all cases.
Page 9
Product Quality
Operating under optimal conditions, trimers content is limited at about 5-15 wt %,
while tetramers are present at the level of only a few thousand ppm. Heavier
oligomers are not produced at detectable levels. Extensive blending studies have
shown that no particular difference is observed between the blending properties
(octane and distillation curve parameters) of an Iso-OctAne stream containing 10%
or less of trimers, and one containing 15% trimers, provided that the tetramers
content is below 10,000 ppm.
The Iso-OctAne and Iso-OctEne product RON and MON are higher than
those of the normal alkylate produced by commercially available alkylation
technologies as shown in the following table:
Table 1: Product Properties
Iso-OctAne
product
Iso-OctEne
product
Normal Alkylate MTBE
Blending RON * 97 103 112 115 97 - 99 116
Blending MON * 94 - 98 93 96 90 - 92 100
RVP (psi) 1.7 1.5 4.5 8.0
Sp. Gravity 0.702 0.728 0.697 0.745
* Base Gasoline RON = 95.0; MON =85.0
RVP of Iso-OctEne/ Iso-OctAne are much lower than that of normal alkylate and
MTBE. This lowers the potential RVP of the gasoline pool, which permits more
butane, isopentane or even more ethanol, to be blended into the gasoline pool.
In those areas where olefins are not severely limited, Iso-OctEne can be blended
directly into the gasoline pool or sold on the market as a high octane and low RVP
blending component.
Page 10
CASE STUDY : Iso-Octene Production In Existing Refinery MTBE Unit
The case study is based on a C
4
feedstock from an FCC unit with 15% Isobutylene
concentration feeding the existing MTBE unit at a rate of 10,000 BPSD. It assumes
that the MTBE plant is US-based and adopts a typical CDTECH MTBE unit
configuration. TBA is used as the selectivator and the revamp is designed in order
to minimize changes to existing equipment and piping.
Reaction conditions can range from 40 to 170F at 5 to 20 barg. This process
utilizes an acidic ion exchange catalyst in the boiling point fixed-bed reactor similar
to the MTBE process. TBA and sec-butanol (SBA) are formed from the reaction of
water with isobutylene and n-butenes respectively. C
8
ether is formed as by-
product from the reaction of butenes with butanols.
The C
4
feedstock is mixed with make-up water and oxygenate recycle and heated
before entering the boiling point reactor, in which, by design, the liquid is heated to
its boiling point by the heat of reaction and a limited amount of vaporization takes
place. Reactor effluent flows to the Iso-OctEne purification section where the
unreacted C
4
hydrocarbons distill overhead. The purification of the Iso-OctEne
product from the oxygenate is accomplished in existing fractionation equipment
after some minor modifications. The pure Iso-OctEne product can be rundown to
storage or fed to a hydrogenation unit for saturation to Iso-OctAne. The selectivator
oxygenate stream is recycled back to the reactor. A methanol recovery section is
not required.
Two major revamping options are available:
Option 1 - Use existing Boiling Point Reactor to achieve a conversion per pass of 80-85% at
dimers selectivities of 90+%. No CDModules are used.
Option 2 Same as option 1 but employ the CD Tower as finishing reactor. This option can
be used to achieve greater than 97% isobutylene conversion with dimer selectivity of 87+%.
Page 11
For option 1, the revamp requires only minor changes to existing equipment and
piping; the only new equipment required is to upgrade the existing CD Tower
reboiler. Option 2 will employ proprietary CDModules to further optimize process
performance. Either option can be used as an effective solution depending on the
refinerys requirements.
Material Balance for Case Study
The overall material balance for the cases are shown in the following table:
Table 2: Material Balance
MTBE Case Revamp Option 1 Revamp Option 2
C4 feed rate Lb/h 86208 86208 86208
Methanol Lb/h 7225 0 0
Water feed Lb/h 20 82 82
C4 Raffinate Lb/h 73583 74115 69720
MTBE Lb/h 19870 0 0
Iso-OctEne Lb/h 0 12175 16570
Iso-OctAne Lb/h 0 0 0
Fuel Gas Lb/h 0 0 0
Product Octane:
RON 116 114 113
MON 100 94 93
(R+M)/2 108 104 103
Economic Comparison for Case Study
The economics for MTBE unit conversion are dependent on a number of factors
including gasoline price, feedstock value, and regulatory environment. Depending
on the processing options available within the refinery, the economics may be
different than presented here. For this paper, we look at the economics of an
MTBE conversion to Iso-OctEne production based on approximate feed and
product prices in November 2001. The values are derived from those published in
October and November issues of Oxy-Fuel News from Hart Publication. They are
summarised in the following table. Utility costs, based on information from one
plant location have been used for the economic analysis and are as follows.
Page 12
Table 3: Feed and Product prices Table 4: Utility Costs
Nov 2001
FCC C
4
feed $/bbl 17.96 600 psig steam $/M lb 2.85
Methanol $/bbl 13.23 Cooling Water $/M gal 0.10
Water $/M gal 4.9 Electricity $/kwH 0.022
C4 Raffinate $/bbl 17.96
MTBE $/bbl 32.46
Fuel Gas $/lb 1.0
Iso-OctEne $/bbl 26.65
Regular Gasoline $/bbl 22.74
Octane Premium $/octane-bbl 0.23
The simple payout for the revamp options of the MTBE unit is summarised in the
following table. Option 2 with catalytic distillation offers better payoff than option 1.
The value for the Iso-OctEne product is $26.65/ bbl based on the Nov 2001
gasoline prices.
Table 5: Economic Summary
Option 1 Option 2
Incremental Investment cost MM US$ 1.37 1.49
Average Annual Operating costs MM US$ 0.68 0.79
Net Profit MM US$ 1.04 1.41
After Tax Profit MM US$ 0.62 0.84
Simple Payout Years 2.2 1.8
Experience
The CDIsoether technology has been fully proven in different combinations of
reactors, selectivators and feedstocks using:
Bench scale reactors
Once-through pilot reactor
Closed-loop process demonstration unit (PDU) located at the Snamprogetti
Research Laboratories in Milan.
Commercial large scale MTBE reactors.
Page 13
Five industrial runs have been carried out worldwide processing the most relevant
C
4
feedstocks and producing more than 5,000 tons of Iso-OctEne/Iso-OctAne, thus
allowing a full characterization of the products.
Conclusions
The CDIsoether technology can be used to process C
4
feedstocks from a wide
variety of sources similar to those processed in MTBE units, i.e. FCC, steam
cracker, or dehydrogenated isobutanes from field butanes. The technology is
highly flexible giving the client an option to continue producing MTBE even after the
revamp. It also enables the refiner to achieve isobutylene conversion and
selectivity to meet overall plant economics.
CDTECHs and Snamprogettis knowledge and unparalleled commercial
experience in production of MTBE and Iso-OctEne provide the most economical
and proven for technologies for octane enhancement. Our technology portfolio
provdes the refiner with flexibility for expanding existing MTBE units as well as
converting MTBE units to Iso-OctEne production. Both products are high quality
gasoline blendstock with low vapor pressure and high octane number.
References
1. Trotta, Roberto; Di Girolamo, Marco; Pescarollo, Ermanno; Marchionna, Mario and Hyland,
Michael J.; High Octane Alkylate from field butanes- The Snamprogetti ISOETHER process
NPRA Annual Meeting 1997 AM-97-54.
2. Trotta, Roberto; Marchionna, Mario; Di Girolamo, Marco; Pescarollo, Ermanno and Hyland,
Michael J.; How to make alkylate without an acid alkylation unit NPRA Annual Meeting
1998 AM-98-51.