Making Premium Alky Late
Making Premium Alky Late
Making Premium Alky Late
UOP offers four alkylation routes, three direct and one indi-
rect route to alkylate.
Presented at
Harts World Fuels Conference
San Antonio, Texas
March 28-30, 2000
MAKING PREMIUM ALKYLATE WITH YOUR MTBE UNIT
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.
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
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.
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
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.
20
15
10
-5
-10
2Q95 2Q96 2Q97 2Q98 2Q99
Source: Hart Publications, Oxy-Fuel News
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
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.
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).
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.
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.
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.
Recycle Methanol
C4 Methanol Unreacted C4
Olefins Recovery Hydrocarbons
Section
Packing
or
Reactor Trays
Section
Methanol
MTBE
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.
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.
H2
Methanol
Dehydrogenation
MTBE
iC4= MTBE
iC4
Mixed C 4s
C4 Isom// C4 Recovery
C4s and Treating
Fractionation
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.
100
M TBE
vol %
50 Alkylate
0
100 200 300 400
T em perature, F
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
Direct
=
C3 Acid Catalyst
=
iC4 + C4
=
C5
Alkylate
Indirect
=
C3
= Acid Catalyst
iC4= + C4 + H2
=
C5
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.
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
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.
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.
102
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.
Catalyst Type
Parameters Resin SPA
iC4= conversion High High
nC4= conversion Minimal Flexible
Water Required Trace
MTBE Produced None None
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.
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.
H2
C3= - C5=
Dehydrogenation InAlk
=
iC4 Alkylate
iC4
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
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.
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.
Recycle Oxygenate
C4 Oxygenate Unreacted C4
Olefins Recovery Hydrocarbons
Section
Light
H2 Ends
Packing
or Trays
Reactor Olefin
Section Saturation
Unit
Alkylate Product
With SPA catalyst, the oxygenate recovery section is not needed. The flow scheme for the
InAlk process with SPA is shown in Figure 10.
C4 Unreacted C4
Olefins Hydrocarbons
Light
H2 Ends
Packing
or Trays
Reactor
Section
Olefin
Saturation Unit
Alkylate Product
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.
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.
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.
Additional
FCC C4s
FCC C4
Stream Direct
InAlk
Alkylation
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
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.
Payback, years 16 2
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.
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.