Fuels For The 21st Century

Fuel Sulfur Solutions Hydrogen Solutions MTBE Solutions Benzene Solutions

Making Premium Alkylate

with Your MTBE Unit
MTBE Solutions
As the future of MTBE remains uncertain, both producers
Meeting Growing Alkylate and users of MTBE are taking a closer look at alkylate.
Demand with Alkylene Alkylate is becoming recognized as the leading contender for
Technology MTBE replacement. From the gasoline producers point of
view, it has the ideal characteristics: It has high octane but no
aromatics, sulfur, or olefins, low vapor pressure and a wide
boiling range. From the MTBE producers point of view, it
has the significant advantage of requiring only a revamp of
an existing MTBE unit.

UOP offers four alkylation routes, three direct and one indi-
rect route to alkylate.

1. The Alkylene process for direct alkylation using a

solid catalyst to avoid the potential issues of a liquid
acid.
2. "Indirect alkylation," a new technology available as
UOP's InAlk process, produces alkylate via a differ-
ent chemistry.
3. Direct alkylation using hydrofluoric acid.
4. UOP also offers the Exxon Sulfuric Acid process for
direct alkylation.
 MAKING PREMIUM ALKYLATE WITH YOUR MTBE UNIT

Jill M. Meister, Brian S. Muldoon, and Dan H. Wei

UOP, LLC
Des Plaines, Illinois

Presented at
Harts World Fuels Conference
San Antonio, Texas
March 28-30, 2000

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 MAKING PREMIUM ALKYLATE WITH YOUR MTBE UNIT

Jill M. Meister, Brian S. Muldoon, and Dan H. Wei

UOP, LLC
Des Plaines, Illinois

INTRODUCTION

There is increasing pressure from the public and environmental regulators to decrease or
eliminate the use of methyl tertiary butyl ether (MTBE) as a gasoline blending component.
MTBE has been blended into gasoline since the late 1970s and is an efficient and economical
way for refiners to meet the regulations for oxygenated or reformulated gasoline (RFG).
However, the water solubility of MTBE is an increasing concern.

The controversy surrounding MTBE may result in reduced use of MTBE in the U.S. and
elsewhere. California has already banned the use of MTBE after December 31, 2002. Removal
of MTBE from the gasoline pool will result in a shortage of octane and an overall decrease in the
volume of gasoline produced. Changes in the gasoline pool from MTBE removal can be
compensated for by increased use of other blending stocks, for example, alkylate1 and isomerate,
which are high-octane paraffinic blendstocks. If oxygenates are still required in gasoline, ethanol
use will increase, however, the higher vapor pressure of ethanol will have to be mitigated. The
increased alkylate demand can be met by several approaches, including the installation of new
alkylation units or revamping existing MTBE units to the UOP Indirect Alkylation (InAlk)
process. The intent of this paper is to discuss some of the technology options available to MTBE
producers should it become uneconomical to continue making MTBE.

MTBE AS A GASOLINE BLENDING COMPONENT

ADVANTAGES OF MTBE

MTBE is a very valuable gasoline blendstock. It has a very high Road Octane of 108, [(RON +
MON)/2], and a moderate Reid Vapor Pressure (RVP) of 8.0 psi (0.6 kg/cm2). These properties
and the fact that MTBE is non-aromatic, non-olefinic, and low in sulfur, make it an excellent

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blendstock in making clean burning gasoline. MTBE is the key oxygenate in producing
oxygenated fuels in the United States.

In 1995, RFG was introduced into areas with air quality problems and has been shown to
significantly improve air quality. California began a more stringent reformulated gasoline
program in the spring of 1996. It should be noted that the maximum air quality benefit is
obtained with older engine technology. Newer engine technology with catalytic converters and
oxygen analyzers produce lower emissions. A study by the University of California at Davis
found that cars with newer automotive emission control technologies showed less benefit from
gasoline with MTBE or other oxygenates than did cars with older emission control
technologies.2

DISADVANTAGES OF MTBE

Given all of the good qualities of MTBE, why is its use being restricted? The major issue is its
water solubility from gasoline, which at 0.55 wt-% is around twice as high as the solubility of
ethyl tertiary butyl ether (ETBE), and tertiary amyl methyl ether (TAME), as shown in Table 1.3
Due to its high water solubility, MTBE has been detected in many ground water sites. MTBE
has been found in over 10,000 sites in California in addition to sites in other states.4 Leaking
underground storage tanks and pipelines, unburned engine exhausts especially from recreational
boating, gasoline spills, and evaporation, are some of the major sources of drinking water MTBE
contamination.

Table 1. Chemical Properties of Ethers

MTBE ETBE TAME

Boiling Point,C (F) 55 (131) 72 (162) 86 (187)
Vapor Pressure, mm Hg at 20 C 240 130 75
Density, g/l 0.74 0.74 0.77
Solubility into H2O from 0.55 0.33 0.24
Gasoline, g/100g H2O

The Environmental Protection Agency (EPA) set the maximum acceptable level of MTBE
in water at 20 to 40 ppb. Most of the identified drinking water contamination levels are less than
20 ppb. Although numerous studies have been performed on the safety of MTBE, none to date
have shown it to cause cancer or other health problems. The California Proposition 65 scientific

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review panel found that, through scientifically valid testing according to generally accepted
principles, MTBE did not cause developmental or reproductive toxicity.5 This panel also found
that there has been insufficient support that MTBE is a carcinogen.5 The problem with MTBE
water contamination is often an objection to the taste of the water. Some people taste and smell
MTBE at levels as low as 2 to 5 ppb.

ECONOMIC VALUE OF MTBE

The worldwide MTBE market has been oversupplied since 1997, and the price of merchant
MTBE has dropped considerably from a premium value to less than its octane value. The
profitability of MTBE production is highly dependent on the product market and on methanol
prices. In late 1996, high methanol prices resulted in a negative margin for MTBE production
(Figure 1). However, the decline in profitability since 1997 is a result of the oversupplied MTBE
market rather than as a result of high methanol prices.

Figure 1. Merchant MTBE Margins

20

15

10

-5

-10
2Q95 2Q96 2Q97 2Q98 2Q99
Source: Hart Publications, Oxy-Fuel News

THE FUTURE OF MTBE

On March 25, 1999 California Governor Gray Davis issued an executive order for the removal
of MTBE from gasoline at the earliest possible date, but not later than December 31, 2002.6 On

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December 9, 1999, the California Air Resources Board (CARB) ordered that the gasoline sold in
the state undergo reformulation to eliminate the use of MTBE by the end of 2002: The new fuel
regulations are designed to help refineries blend substitute additivesmost likely ethanolwhile
maintaining air quality.7 The United States EPA Blue Ribbon Panel issued findings in July,
1999 calling for a significant reduction of MTBE use in U.S. gasoline.3 As a result of negative
publicity from California and because of water contamination in other areas outside of
California, it is likely that there will be a further reduction of MTBE use in the U.S. The
uncertainty about MTBE has resulted in many new MTBE projects being placed on hold, or
converted to a different product, like alkylate.

GASOLINE FORMULATION CHANGES

Worldwide gasoline specifications are continuing to move toward cleaner burning gasoline.
Changes in RVP as well as reductions in olefins, sulfur, benzene, aromatics, and distillation are
underway. All of these changes must be met while maintaining or increasing gasoline octane. In
addition, new emerging engine technologies will require further changes in fuel requirements.
As a result, refiners must evaluate their available blendstocks and refinery configurations to
determine how they can best produce gasoline to meet market demands and new specifications
for cleaner gasoline.

IMPACT OF REMOVING MTBE

Removing MTBE from U.S. gasoline will result in a 3 to 4 % deficit in gasoline. The U.S.
MTBE demand represents 66% of the worldwide total. California represents 37% of the U.S.
MTBE demand.8 In addition, removing MTBE results in an octane shortage. Since MTBE is a
light boiling component, it may be difficult for refiners to meet the gasoline distillation
specifications as well as the proposed Driveability Index specification (DI).

DI = 1.5*T10 + 3*T50+ T90

Removing MTBE also results in the loss of a non-aromatic, non-olefinic, low sulfur
blendstock, which will make it even more difficult to produce cleaner burning gasoline. The
major gasoline blending streams used to meet all of the specifications are:

Reformate produced from a reforming unit that converts naphtha into a high-octane
product containing aromatics and benzene. Hydrogen is a valuable by-product from
the reforming process.

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 FCC naphtha produced from an FCC unit by cracking gas oil. This stream contains
sulfur, olefins, and aromatics.
Isomerate results from isomerization of C5 and C6 paraffins to increase octane. It
can have a high RVP depending on composition.
Oxygenates includes ethers produced from refinery C 3 to C5 olefins or ethanol
fermented from agricultural material. Oxygenates can have water solubility,
blendability, and/or high RVP problems.
Alkylate produced from C3 to C5 olefins. Alkylate consists of high-octane branched
paraffins and has a low RVP, between 2 and 4 psi.

The combination of isomerate and alkylate is a good replacement for MTBE because
together they have a high octane and a broad distillation range which brackets MTBE. Since
both are paraffinic, they are ideal components for clean burning gasoline.

ALTERNATIVES TO MTBE PRODUCTION

There are two major routes to MTBE: 1) from olefins produced by an FCC unit, steam cracker,
or propylene oxide manufacture; 2) from butane that is dehydrogenated in a dehydrogenation
unit. Before discussing alternatives to making MTBE, a brief review of MTBE production from
C4 olefins and from butane is necessary. A typical MTBE unit flow scheme is shown in Figure
2.

Figure 2. Typical MTBE Unit Flow Scheme

Recycle Methanol

C4 Methanol Unreacted C4
Olefins Recovery Hydrocarbons
Section

Packing
or
Reactor Trays
Section

Methanol
MTBE

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 MTBE FROM C4 OLEFINS

UOPs MTBE technology is the Ethermax process. The Ethermax process normally uses one
or two adiabatic fixed bed reactors followed by RWD, a catalytic distillation column. The
RWD column uses KataMax packing to obtain very high conversion. Details regarding the
design and operations of KataMax packing in MTBE production have been discussed
elsewhere.9 An oxygenate recovery section is used to recover unconverted methanol, which is
then recycled back to the reactor section.

MTBE FROM BUTANE

A butane dehydrogenation unit is used to convert field butanes to iso-butene for merchant
MTBE production. The process configuration is shown in Figure 3. The UOP MTBE complex
includes a Butamer/DIB section, Oleflex unit, and MTBE Ethermax unit. Details regarding
design and operation of these complexes have been discussed elsewhere.10 The MTBE unit flow
scheme is similar to the one shown in Figure 2. The MTBE complex can include other butane
dehydrogenation, isomerization, or etherification technologies.

Figure 3. Dehydrogenation Based MTBE Complex

H2
Methanol

Dehydrogenation
MTBE
iC4= MTBE
iC4

Mixed C 4s
C4 Isom// C4 Recovery
C4s and Treating
Fractionation

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ALTERNATIVES

In light of market pressure, current MTBE producers have several choices:

Continue making MTBE

Shutdown the unit
Produce chemical grade iso-butene or other butene chemical derivatives
Revamp the dehydrogenation unit to produce propylene
Produce ETBE or TAME
Produce alkylate via:
HF or H2SO4 alkylation technology
UOP Alkylene process (solid acid technology)
UOP Indirect Alkylation (InAlk) process

Current economics favor continued MTBE production. However, as MTBE is phased out of
gasoline, some MTBE producers may choose to shutdown their units and get out of the business.
Many merchant MTBE producers will probably be interested in finding an alternate use for their
plants. The market for chemical grade iso-butene or other butene chemical derivatives is an
option, although it is relatively small and the world market would be oversupplied if one
merchant MTBE producer converted to this option. Producing propylene, ETBE or TAME
would result in varying degrees of additional investment. Demand for ETBE and TAME is
uncertain as both may suffer from the same solubility and public perceptions as MTBE. In
addition, the health and safety of these two ethers is less understood than MTBE. Refinery and
merchant MTBE producers need to evaluate their location, product slate, and the impact on
other process units that would result from changes to their MTBE units.

ADVANTAGES OF ALKYLATE

Alkylate is a non-aromatic, non-olefinic, low sulfur, low RVP, high octane, paraffinic
blendstock. These properties make it an ideal component for blending into the gasoline pool. In
addition, alkylate has a wide boiling range as shown in Figure 4. If alkylate replaces MTBE,
lighter materials, such as isomerate and/or pentanes, which are becoming more difficult to keep
in the gasoline pool as RVP specifications are lowered, can be used in the blend.

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 Figure 4. Boiling Point Distribution

100
M TBE

vol %
50 Alkylate

0
100 200 300 400
T em perature, F

ALKYLATE PRODUCTION ROUTES

There are two routes to producing alkylate, which UOP calls direct alkylation and indirect
alkylation. Direct alkylation is the reaction of iso-butane with light olefins in the presence of an
acid catalyst (Figure 5). Direct alkylation occurs in several technologies that use well-known
carbocation chemistry. These processes either use the liquid acids, HF or H 2SO4, or use a solid
catalyst, as is used in the Alkylene process. Details of direct alkylation and the Alkylene process
have been discussed in other publications.11

Figure 5. Alkylation Chemistry

Direct
=
C3 Acid Catalyst
=
iC4 + C4
=
C5
Alkylate
Indirect
=
C3
= Acid Catalyst
iC4= + C4 + H2
=
C5

Indirect alkylation involves sequential olefin oligomerization (polymerization) and

hydrogenation reaction steps, which is the basis of the InAlk process. Polymerization reactions

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are catalyzed by a moderate-acid catalyst, such as solid phosphoric acid (SPA)12 or sulfonic ion
exchange resin.13 Both of these catalysts have been used for many years in refineries and
petrochemical plants.

Examples of the indirect alkylation reactions with butene feedstocks are shown in Figure 6. The
C4 olefins are reacted over the polymerization catalyst under mild conditions, which mainly
results in a mixture of branched C8 alkenes. The polymerization reaction determines the extent
of branching in the final product. After hydrogenation, a high-octane C8 paraffinic gasoline
blendstock is produced that is similar to traditional alkylate. The branching of the C8 alkenes
during polymerization is the key step in optimizing alkylate quality.

When the feedstock is rich in iso-butene, such as the product from an iso-butane
dehydrogenation unit, careful selection of reaction conditions results in the major product being
2,4,4-trimethylpentene (2,4,4-TMP=). After hydrogenation the paraffinic product has an octane
rating of 101 to 102 RON. High octane results from maximum branching of the product alkanes
to form 2,2,4 and 2,2,3 trimethylpentane. Control of the reaction conditions minimizes the
isomerization to low octane isomers, such as dimethylhexane.

Figure 6. InAlk Chemistry

C C C
+H 2 2,2,4 Trimethylpentane
C-C-C + C-C-C ----> C-C-C-C = C ----------->
C C
RONC = 100, MONC = 100

C C
+H 2 2,2,3 Trimethylpentane
C-C = C-C + C-C-C ----> C-C-C-C = C -------->
RONC = 109.6, MONC = 99.9
CC

CC
+H 2 3,4 Dimethylhexane
C-C = C-C + C-C = C-C ----> C-C-C-C-C = C ---->
RONC = 76.3, MONC = 81.7

High-octane products can also be formed when processing mixed iso-butene and n-butene
feedstocks, such as those produced from refinery FCC units. The desirable reactions are
polymerization of iso-butene with either n-butene or another iso-butene. Low-octane
dimethylhexene is formed from the polymerization of the n-butene components. Conversion of

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C3 and C5 olefins to a high-octane product can also occur in the polymerization section at select
conditions.

Controlled processing conditions are again important since the typical product from
polymerization units tends to have more low-octane dimethylhexene components than
high-octane trimethylpentenes. Depending on the degree of n-butene conversion achieved, the
alkylate octane from FCC-derived feedstocks can range from 95 to 100 RON after
hydrogenation.

INALK TECHNOLOGY

The InAlk process converts olefinic feeds to alkylate in two steps, polymerization and
hydrogenation. Adding a dehydrogenation unit with an optional butane isomerization unit to the
InAlk process results in an InAlk complex that provides greater feedstock flexibility.

INALK PROCESS

The InAlk process offers refiners considerable processing flexibility. The polymerization and
hydrogenation sections use different catalysts. There is a choice of catalyst for each step, which
depends on the feedstock properties to the InAlk process as well as the processing objectives.

Polymerization Section

The polymerization step uses a moderate acid catalyst, either resin13 or SPA.12 The reaction
conditions are selected to maximize production of highly branched isomers. The InAlk process
allows refiners to convert C3 to C5 olefins to a high quality product. The amounts of iC4= versus
other olefins converted must be optimized for each situation and the benefit of processing
additional olefins must be evaluated. When the polymerization feed is very rich in iso-butene,
careful processing results in 2,2,4-trimethylpentane (2,2,4-TMP) as the major product from the
InAlk process.

Resin

Resin catalyst is used in nearly all MTBE units. Resin catalysts are synthetic, organic
crosslinked, sulfonated, cation-exchange resins. The most common resin is polystyrene
crosslinked with divinylbenzene. There are differences between making MTBE and TMP=. The
key for producing both products is maintaining good selectivity while getting good per pass
conversion. The iC4= conversion has a lower once-through conversion to TMP= than to MTBE.

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Increasing the iC4= conversion across the resin catalyst for TMP= production causes an increase
in the amount of C12+ material produced.

The InAlk process is operated to limit production of C 12+ components to less than 10% of
the product. Achieving a similar iC4= conversion for TMP= as MTBE requires a different process
design or set of operating conditions. The desired conversion can be obtained in a number of
ways via a recycle loop of unconverted iC4=; a recycle loop of an iC4= side product like MTBE;
using many additional reactors; using an isothermal reactor; or using RWD technology. All of
these options result in higher investment costs for new units or additional investment to revamp
the existing MTBE unit.

If a heavier product can be accepted, then a higher iC4= per pass conversion can be
obtained. Resin catalysts do not have good activity for nC4= conversion. As a result, to get good
selectivity the nC4= conversion is limited to less than 10%. Resin catalyst will have a lower
catalyst life producing TMP= than in MTBE service due to fouling of the catalyst with high
molecular weight polymer.

SPA

SPA catalyst has been used for many years in motor fuel and cumene catalytic condensation
units as well as in other technologies. SPA catalyst provides flexibility because nC4= conversion
can be varied from 30 to 80%. Iso-butene plays a major role in producing highly branched
products. As more iC4= is converted relative to nC4=, more TMP= is produced. Increased TMP=
production results in higher alkylate octane after hydrogenation (Figure 7).

A mixed iso-butene and n-butene feed can also produce a high-octane product in the InAlk
process. For instance, when 80% of the n-butenes and 96% of the iso-butenes are converted, the
major product is 2,3,4-TMP=. This occurs because the 2,4,4- and 3,4,4- TMP= isomers that are
formed initially are isomerized to 2,3,4-TMP = and only low levels of dimethylhexenes are
formed.

Catalyst life for SPA catalyst in the InAlk process is expected to be more than 18 months,
which is longer in terms of (gal of product)/(lb of catalyst) than the catalyst life in the UOP
Catalytic Condensation process for cumene or for motor fuel. The catalyst lasts longer in the
InAlk process because of its much less severe and optimized operating conditions, which
dramatically reduces the rate of catalyst coking and increases useable catalyst life. Data shows
that because the rate of coke laydown on both resin and SPA catalyst are about the same, their
useable life is similar.

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 Figure 7. Effect of Iso-butene on Octane

102

100 Butane Feed

FCC Olefins
with Dehydro
98 with Dehydro
R
O 96
Refinery
N
94 FCC Olefins

92

90
= =
iC4 :nC4 Butene Reaction Ratio

In addition to deactivation from coking, SPA catalyst like resin catalyst deactivates from
feed contaminants and polymer fouling. Some feed contaminants, such as oxygenates or basic
compounds, will neutralize the acid sites and cause deactivation.

Water is added to both resin and SPA catalyst systems to control the activity and selectivity
of the operation. The resin catalyst system requires more water addition than the SPA catalyst
system to ensure proper resin activity and selectivity.

A comparison of the resin and SPA polymerization catalysts is shown in Table 2.

Table 2. Polymerization Section Catalyst Comparison

Catalyst Type
Parameters Resin SPA
iC4= conversion High High
nC4= conversion Minimal Flexible
Water Required Trace
MTBE Produced None None

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Hydrogenation Section

UOP has extensive experience in hydroprocessing technologies. Two different olefin saturation
catalysts have been developed for the InAlk process. One catalyst contains a noble metal; the
other uses a non-noble metal. The noble metal catalyst has been used in the petrochemical and
refining industries for saturation of olefinic streams similar to the InAlk product. Noble metal
catalysts, however, require a low level of feed contaminants to be effective. The primary
advantage of the noble metal catalyst is that the total installed cost will be lower than with
non-noble metal catalyst because no recycle hydrogen is required.

The non-noble metal catalyst has been widely used in commercial hydroprocessing
applications in the refining industry. The primary advantage of this catalyst is that it is robust
and generally insensitive to contaminants. However, the capital cost is higher due to the need for
sufficient hydrogen.

Under appropriate operating conditions in the hydrogenation section, no hydro-

isomerization or cracking occurs and the product bromine number is less than one. The selection
of the best hydrogenation scheme depends on feedstock and other site-specific factors. In
general, the non-noble metal catalyst is most attractive in refinery applications when converting
MTBE units to the InAlk process, while the noble metal catalyst is best applied in converting
MTBE complexes or chemical industry MTBE units to the InAlk process.

INALK COMPLEX

The InAlk complex adds a dehydrogenation unit (Oleflex) to the InAlk process. A butane
isomerization process (Butamer) can be integrated into the process to further increase alkylate
production from n-butane as shown in Figure 8.

The InAlk complex produces alkylate from butanes. The process may be located adjacent to
the LPG recovery unit at an oil or gas field facility, or it may be associated with a refining or
petrochemical complex. In the InAlk complex, feedstock may be supplemented by light olefins
ranging from propylene to pentenes. An advantage of the InAlk complex is that it does not
require the 1:1 ratio of iso-butane to alkenes necessary for direct alkylation processes. This
provides the producer flexibility in choosing feedstocks.

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 Figure 8. InAlk Complex

H2

C3= - C5=

Dehydrogenation InAlk
=
iC4 Alkylate
iC4

Mixed C4 Isom/ C 4s C4 Recovery

C4s Fractionation and Treating

Dehydrogenation Section

Integration in the InAlk complex allows a significant simplification of the Oleflex process for
butane dehydrogenation. The Oleflex process selectively converts propane to propylene or
iso-butane to iso-butene. It is the most advanced of various light hydrocarbon dehydrogenation
processes that date back to the 1930s.14 Nine Oleflex units are operational, and more are in
design or construction. While the Oleflex section in an MTBE complex can be used for alkylate
production without modification, UOPs knowledge gained from over fifty operating years of
commercial Oleflex experience and process optimization enable a dehydrogenation section
design that is specific for the InAlk process. The new design is lower in cost because it employs
two reactors and two heaters, compared to the Oleflex process for MTBE production with three
reactors and three heaters. Additional improvements are achieved from the efficient use of
hydrocarbon streams available in the InAlk complex and from using a Recovery Plus system
for hydrogen recovery. The specific dehydrogenation section for the InAlk process has been
described in other publications.15

EVALUATION OF MTBE REVAMP OPTIONS

Stand-alone units within refineries or merchant dehydrogenation-based MTBE complexes can

be revamped to InAlk service. Reuse of existing equipment is desired to minimize capital. The
MTBE reactors, butene column, pumps and heat exchangers can be reused. The InAlk process
can use either tubular or adiabatic reactors. The existing butene column can be reused with

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modifications to the reboiler to separate the C4 saturates and unreacted C4 olefins from the C5+
iso-olefins formed in the InAlk process. The unreacted material, or raffinate, is produced from
the column as an overhead stream. The C5+ iso-olefins are produced as a column bottoms
product and are sent to the hydrogenation section.

The olefin feed to the MTBE unit in a refinery is normally water washed to remove basic
compounds that would poison the catalyst. Since the InAlk unit also uses an acid catalyst it
requires similar feed treatment; the current feed treatment procedures should be adequate for the
InAlk process.

Two options for revamping to InAlk service will be evaluated. 1) Converting an MTBE
complex to InAlk service with either resin or SPA. 2) Converting a refinery MTBE unit to InAlk
service with either resin or SPA. When looking at the refinery MTBE unit conversion it is
necessary to consider the impact on the refinerys direct alkylation unit.

ECONOMIC BASIS

The feed and product prices used for the economic comparison for the revamp examples are
given in Table 3. The alkylate price depends on its octane value. The equation for determining
the alkylate price is:

(Unleaded regular gas price) + (Alkylate Road Octane 87) * (Value of an octane barrel)

The values assumed for an octane barrel and for unleaded regular gasoline are
$0.25/(octane barrel) and $18.90/barrel, respectively.

Table 3. Pricing Basis

FCC Butenes, $/bbl 16.37

Field Butanes, $/bbl 10.37
Methanol, $/bbl 13.29

MTBE, $/bbl 28.76

Propane, $/bbl 13.28
Hydrogen, $/lb 0.33
Fuel Gas, $/MMBTU 2.10

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 For the economic analysis, the variable production cost takes into account the yearly cost of
feedstock and utilities as well as the yearly-normalized catalyst cost. All production and
investment costs, and revenue for revamp to the InAlk process are calculated as increments from
when the unit was making MTBE. The fixed production cost takes into account the delta costs
from the existing process in terms of labor, maintenance, overhead, and interest. In addition, the
fixed production cost includes the interest on working capital. The working capital was
calculated using 15 days of feedstock and product in inventory. The after-tax profit is calculated
using the delta gross profit from the base case then subtracting from this amount straight-line
depreciation and taxes which are 40%. The simple payback is determined by the incremental
capital investment cost divided by the incremental after-tax profit.

MTBE COMPLEX REVAMP

The unit considered is a world-scale butane dehydrogenation MTBE complex (Figure 3), based
on the Oleflex process. This complex, located on the U.S. Gulf Coast, includes a Butamer/DIB
section, an Oleflex unit, and a MTBE Ethermax unit. The conversion of the MTBE complex to
the InAlk complex involves revamping the MTBE Ethermax process and adding a
hydrogenation section. This producer was concerned about sulfur breakthrough from the
dehydrogenation reactor effluent dryers; therefore, the non-noble metal catalyst was used for the
hydrogenation section.

If resin catalyst is used, the reactor section from the existing MTBE unit can be reused. The
oxygenate recovery section is reused to recover the oxygenate used to attenuate and hydrate the
resin. An olefin saturation unit is added to convert the bottoms from the butene column to
alkylate. The flow scheme is shown in Figure 9.

Figure 9. MTBE Revamp to InAlk with Resin

Recycle Oxygenate

C4 Oxygenate Unreacted C4
Olefins Recovery Hydrocarbons
Section

Light
H2 Ends
Packing
or Trays
Reactor Olefin
Section Saturation
Unit

Alkylate Product

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 If SPA catalyst is used, the existing reactor volume is usually sufficient to achieve high
conversion of iso-butene. If conversion of normal butenes is desired, then additional catalyst
volume is required. In this example, the producer wanted flexibility in normal butene
conversion so new reactors were incorporated.

With SPA catalyst, the oxygenate recovery section is not needed. The flow scheme for the
InAlk process with SPA is shown in Figure 10.

Figure 10. MTBE Revamp to InAlk with SPA

C4 Unreacted C4
Olefins Hydrocarbons

Light
H2 Ends
Packing
or Trays
Reactor
Section
Olefin
Saturation Unit

Alkylate Product

Material Balance for MTBE Complex Conversion

The material balances for the MTBE and InAlk complexes are shown in Table 4. The product
octane shown can vary somewhat depending on the flow scheme and overall conversion desired.

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 Table 4. Material Balance for MTBE Complex Conversion

MTBE Complex InAlk Complex

with Resin with SPA
Field butanes, BPSD 17,570 17,570 17,570
Methanol, BPSD 6,030 - -

MTBE product, BPSD 17,700 - -

Net hydrogen, lb/hr 2,880 1,665 1,445
C5+ alkylate product, BPSD - 11,570 11,850
Product properties
RONC 118 99 101
MONC 100 97 96
(RON+MON)/2 109 98 99

Economics for MTBE Complex Conversion

Revamping an MTBE complex to InAlk service results in a simple payback of less than a year
for the additional capital investment (Table 5). The expected future case assumes that there will
be limited demand for MTBE and its value will be zero. The product revenue for the InAlk cases
is $102 MM per year based on the feed and product values presented in Table 3. Additionally,
the value of alkylate from the InAlk process using resin based on a 98.3 Road Octane is valued
at $21.71 per barrel. With SPA catalyst, alkylate is valued at $21.80 per barrel based on a 98.6
Road Octane.

Table 5. Economics for MTBE Complex Conversion

MTBE Complex MTBE Complex InAlk Complex

Today Expected Future with Resin with SPA
Revenue, $MM/yr 189 0 102 102
Capital investment cost, $MM - - 7.7 7.0
Variable production cost, $MM/year 99 - 67 66
Fixed production cost, $MM/year 1 0 1 1

After tax profit, $MM/year 53 0 19 20

Payback, years 0.4 0.3

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REFINERY MTBE UNIT REVAMP

The unit considered is a refinery-based MTBE unit fed by an FCC unit and is based on the
MTBE Ethermax process shown in Figure 2. This unit is located on the U.S. West Coast. The
material balances in Table 6 include the downstream alkylation unit because the MTBE or InAlk
unit and the alkylation unit operate together to optimize C 4 olefin processing. In this case, the
same quantity of olefins was processed in the direct alkylation unit as in the MTBE production
case, because the direct alkylation unit could not be expanded. The nC4= converted in the InAlk
process frees up capacity in the direct alkylation unit which can then be used to process
additional olefins (Figure 11). Similar to the conversion of the MTBE complex, the assumption
is made that the future value of MTBE will be zero. The resin and SPA catalyst options were
evaluated. The non-noble metal catalyst system for the hydrogenation section was required for
the refinery-based MTBE unit because of higher feed sulfur levels.

One of the advantages of converting the MTBE unit to InAlk service is that it enables
increased C4= utilization. This is a result of the ability of the InAlk process to convert nC4= and
not just iC4=. The nC4= conversion can be varied from 30 to 80% across the SPA catalyst. New
polymerization reactors were used for the SPA catalyst case in order to achieve the normal
butene conversion flexibility.

Figure 11. Integrated C4 Olefin Processing Scope

Additional
FCC C4s
FCC C4
Stream Direct
InAlk
Alkylation

C5+ Product Stream

Material Balance for MTBE Unit Conversion

The material balances for the MTBE and InAlk units are shown in Table 6. In all cases, because
the direct alkylation unit could not be expanded, the total amount of olefins to the direct

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alkylation unit was maintained at the same rate as in the MTBE base case. Note, however, that
the InAlk process can handle more C4 olefins than the MTBE process. The producer has
additional olefins available to make additional alkylate. With both resin and SPA catalyst, more
FCC olefins can be converted with InAlk than with the MTBE process. More alkylate is
produced with SPA then resin because of its greater ability to convert n-butene. The higher
conversion of normal butenes with SPA results in similar octane numbers for the resin and SPA
cases.

Table 6. Refinery Alkylate Production after MTBE Unit Conversion

Alkylation Unit InAlk with Resin InAlk with SPA

With No MTBE
FCC C4 stream, BPSD 15,720 16,940 18,120
Methanol, BPSD 910 - -

Hydrogen, lb/hr - 500 640

MTBE product, BPSD 2,670 0 - -

+
C5 alkylate product, BPSD 10,150 12,425 13,010
Product properties
RONC 96 97 97
MONC 94 94 94
(RON+MON)/2 95 96 96

Economics for MTBE Unit Conversion

For the revamp of the MTBE unit to InAlk service, the incremental capital investment and
product revenue resulted in a simple payback of two years with SPA catalyst. Unlike the
conversion of the MTBE complex, using SPA catalyst is much more attractive than using resin
catalyst. This is due to the n-butene conversion flexibility that the SPA catalyst offers. Product
revenue is greater than $90 MM per year for both InAlk cases based on the feed and product
values presented in Table 3. Additionally, the value of the alkylate blend from the InAlk and
alkylation units based on a 95.6 Road Octane is $21.05 per barrel. The value of alkylate from
the alkylation unit alone based on a 95.3 Road Octane is $20.96 per barrel.

Table 7. Economics for Refinery MTBE Unit Conversions

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 Alkylation Unit InAlk with Resin InAlk with SPA
Expected Future
Revenue, $MM/yr 89 93 99
Capital investment cost, $MM - 4.8 4.4
Variable production cost, $MM/year 71 73 76
Fixed production cost, $MM/year 1 1 1

After tax profit, $MM/year 10 - -

After tax delta profit, $MM/year - 0.3 2

Payback, years 16 2

REVAMP IMPLEMENTATION STRATEGY

The most economical way to revamp an MTBE unit to InAlk service is to reuse as much of the
existing equipment as possible. However, from a production point of view, this may not be the
optimal way to proceed with the revamp. For example, if additional catalyst volume is needed,
building new polymerization reactors and then dropping them on the existing foundations might
allow the quickest and most economical turnaround. Also, building a new olefin saturation
section will allow the existing unit to continue operating without interruption. The
hydrogenation section could be built on-site or as a module that can be shipped to the site.

COMMERCIAL STATUS

UOP has completed one Basic Engineering Design Package for the InAlk process and has two
more InAlk process units currently in design. In each of these projects, the InAlk technology was
chosen over competing technologies as a replacement for MTBE production. Two of these units
use SPA catalyst in the polymerization section. The third unit is a revamp of an existing MTBE
unit, which, because of its particular processing objectives, will use both resin and SPA catalyst
in the polymerization section.

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 CONCLUSIONS

Concerns over MTBE contamination of drinking water have lead to interest in alternative
processing routes for the C4 olefins used to produce MTBE. The InAlk process is an
economically viable alternative for converting butenes to a high quality gasoline-blending
component rich in trimethylpentanes that have octanes of 100 RONC or more. The alkylate
product has ideal characteristics; high octane with no aromatics, sulfur, or olefins and low vapor
pressure.

The InAlk process is capable of processing a wide range of C4 feedstocks from FCC and
steam cracker light olefin streams to field butanes (with an associated Oleflex process), giving
the producer maximum flexibility in feedstock selection. Low-value field butanes can be
efficiently converted to alkylate via an InAlk complex. The InAlk technology is also a low-cost,
simple revamp for existing dehydro-based MTBE complexes and refinery MTBE units.

UOPs analysis of the revenues and production costs of MTBE indicates that currently,
continued production of MTBE is much more economical than converting these units to alkylate
production. However, the growing demand for alkylate for California, coupled with resistance
to continued large scale use of MTBE, will make conversion to the InAlk process an
increasingly attractive option for MTBE producers.

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 REFERENCES

1) California Energy Commission, Supply and Cost of Alternatives to MTBE in Gasoline,

February, 1999.
2) University of California at Davis, Health and Environmental Assessment of MTBE,
Report to the Governor and Legislature of the State of California as Sponsored by SB 521,
November 12, 1998.
3) Environmental Protection Agency (EPA), Achieving Clean Air and Clean Water: The
Report of the Blue Ribbon Panel on Oxygenates in Gasoline, September 15, 1999.
4) CBS News, 60 Minutes, January 16, 2000.
5) California Environmental Protection Agency (EPA), California Prop 65 Scientific Review
Panel Report on MTBE, News release, Dec 10, 1998.
6) Davis, Governor of California, Executive Order D-5-99, March 25, 1999.
7) C. Bowman, Phaseout of MTBE approved: State anti-smog panel orders changes in gas,
December 10, 1999.
8) California Energy Commission, Report on the Current Oxygenate Market, October 1998.
9) S. L. Krupa and B. S. Muldoon, RWD Technology for High-Conversion Ether
Production, Engineering Foundation Conference, Davos, Switzerland, October 26-31,
1997.
10) R. A. Pogliano, M. A. Krawczyk, B. V. Vora, and J. H. Gregor, Dehydrogenation-Based
Ether Production, 1996 Petrochemical, DeWitt & Company, Houston, March 19-21, 1996.
11) S. M. Black, C. D. Gosling, K. Z. Steigleder, and D. J. Shields, Meeting Growing Alkylate
Demand with Alkylene Technology, NPRA Annual Meeting 2000, San Antonio, March
26-28, 2000.
12) G. Egloff and R. F. Davis, Polymerization of Mono-Olefins with Solid Phosphoric Acid,
XII International Congress of Pure and Applied Chemistry, New York, September 10-13,
1951.
13) W. O. Haag, Oligomerization of Isobutylene on Cation Exchange Resins, Chemical
Engineering Progress Symposium Series, No. 73, Vol. 63.
14) J. H. Gregor, J. E. Zimmerman, and P. R. Cottrell, Selective Hydrogenations and
Dehydrogenations, DGMK Petrochemical Division Second Technical Conference, Kassel,
Germany, November 11-12, 1993.
15) D. H. Wei, H. U. Hammershaimb, J. M. Meister, and H. Abrevaya, New Route to Produce
High Octane Gasoline, AIChE Annual Meeting, March, 2000.

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