Olefin Transformation - A Means to Ease Your MTBE Woes

Daniel J. Weidert – ABB Lummus Global Inc.

Prepared for

AIChE 2000 Spring Meeting

March 5-9, 2000

Light Ends Processes II – Session T9021

Unpublished

AIChE Shall Not Be Responsible For Statements or Opinions Contained in Papers or

Printed in its Publications

Introduction

The oxygen mandate by government regulatory agencies was the cornerstone in their
mission for the production of cleaner burning gasoline. As a result, the oxygenated fuels
industry expanded swiftly over the last decade as a means to achieve the targeted levels
of oxygen content and to supply an octane enhancement ingredient for gasoline. MTBE
was the overwhelming choice of many refiners to satisfy the oxygen content
specification. In addition, environmental regulators worldwide reduced the maximum
acceptable RVP specification for gasoline, limiting the refiner’s ability to blend
significant quantities of C4s into gasoline. The production of MTBE was an economical
alternative. By reacting high vapor pressure isobutylene with methanol to produce
MTBE, a low value C4 became a value-added product with high-octane value and low
vapor pressure characteristics that added to the overall volume of the gasoline pool.

Ironically, the state government regulatory agency that initiated the drive towards the
production of oxygenates is now mandating the removal of MTBE from gasoline.
Momentum is currently building towards the elimination of MTBE from gasoline. With
the potential for the MTBE market to diminish as swiftly as it developed, MTBE
producers are left scrambling to find alternative C4 processing options.

Finding a profitable, alternative use for isobutylene previously targeted for MTBE
production is facility-specific and dependent upon existing processing strategies within
the facility as well as the availability of other potential feed materials. One possible
derivative that is not usually associated with C4 processing is propylene, which is mainly
used for polypropylene production. Demand for propylene is consumer driven, unlike
MTBE, which was superficially built on the shifting foundation of environmental
regulations. Polypropylene continues to make inroads into the large volume polyethylene
market as an economical alternative for plastic products. Given this inroad, propylene
demand is expected to grow by 5.5% over the next several years and exceed ethylene
demand by approximately 1%.

A recent trend in many refineries with FCC units is downstream integration for propylene
supply to polypropylene units. Currently, approximately 70% of worldwide propylene
production are from ethylene plants with most of the balance from FCC off-gases. A
small percentage of propylene is produced via propane dehydrogenation or
ethylene/butene metathesis. The addition of new ethylene plant capacity will not satisfy
demand for propylene since substantially more ethylene is produced per unit of feed than
propylene. Alternative methods will be required to meet this demand.

Propylene Production through Olefins Conversion

ABB Lummus Global’s (Lummus’) portfolio of technologies contains a unique

combination of commercially proven processes that offer the capability to produce
propylene from the isobutylene. The keystone of this combination is Olefins Conversion
Technology (OCT), which utilizes metathesis (disproportionation) for the interconversion
of light olefins. Metathesis is an equilibrium reaction between two olefins where the
double bond of each olefin is broken to form intermediate reactants. These intermediates
recombine to form new olefin products. Some disproportionation reactions utilizing C4
olefins are:

• 1-butene with itself to form ethylene and 3-hexene;

• 1-butene and 2-butene to form propylene and 2-pentene;
• 2-butene and ethylene to form propylene.

This discussion will concentrate on the third reaction shown above.

The butene/ethylene metathesis to propylene consists of the following reaction:

CH3—CH=CH—CH3 + CH2=CH2 Ù 2 CH2=CH—CH3

2-Butene + Ethylene Ù 2 Propylene

In addition, an isomerization reaction also occurs in the system.

CH2=CH--CH2--CH3 Ù CH3—CH=CH—CH3
1-Butene Ù 2-Butene

These are vapor phase reactions occurring in a fixed bed reactor under essentially
isothermal conditions. Equilibrium metathesis conversion ranges from 65 to 70% of the
butenes with propylene selectivity ranging from 90 to 98%. Optimal conditions are
achieved by adjusting the temperature, pressure, and ethylene-to-butene ratio for various
design considerations. Essentially two thirds of the propylene is produced from low
value butenes and when coupled with low capital cost results in excellent economics for
the production of propylene.
A simple block flow diagram for OCT is shown in Figure 1. Recycle ethylene and
butene are combined with fresh ethylene and butene and pretreated to remove catalyst
poisons. The pretreater effluent is vaporized and superheated by cross exchange with the
hot reactor effluent. In the reactor, catalyst promotes the reaction of 2-butene and
ethylene to propylene and simultaneously isomerizes 1-butene to 2-butene. The product
from the reactor is cooled and sent to the fractionation section to recover polymer grade
propylene product and ethylene and butene for recycle. Light reaction by-products are
purged from the system while heavy reaction by-products are removed as a slipstream
and can be mixed in the gasoline pool. This process can be integrated with existing
facilities to increase operating efficiency and reduce capital expenditure.

Figure 1 - Olefins Conversion Technology

Ethylene + Butene Propylene

Ethylene
Triolefins Triolefins
Pretreatment Preheat Reactor
Butene

Product
Fractionation
Ethylene/Butene Gasoline
Recycle

Propylene Product
Purges

Phillips Petroleum Company originally developed Olefins Conversion Technology. In

1997, Lummus acquired OCT with exclusive rights to license OCT for C2 to C5 olefins.
This proven, low capital cost approach has been demonstrated on a commercial scale
with various metathesis applications.

The original unit was developed for Shawinigan Chemicals Ltd. of Canada to perform the
reverse reaction of producing ethylene and butenes from propylene. The unit operated
successfully from 1965 to 1972 until it was shutdown for economic reasons. Phillips
Petroleum Company designed another OCT application to produce neohexane and
isobutylene from ethylene and diisobutylene using the same metathesis catalyst.
Lummus designed a unit to convert ethylene to propylene by combining the dimerization
of ethylene to butene with the metathesis of ethylene and butene. This unit was put into
operation at Lyondell Petrochemical Company (Equistar) in June of 1985 and Lummus
expanded the unit’s capacity in 1992.
Two recent awards are currently in the engineering phase. The first unit will combine
OCT with Lummus’ patented, low pressure FCC Off-gas Recovery System within an
existing refinery in Europe. Ethylene recovered from FCC off-gas will be reacted with n-
butenes currently feeding an alkylation unit. The second unit will be fully integrated with
a grassroots steam cracker for BASF-Fina.

Ethylene Feedstock for the OCT Unit

Three common sources for ethylene feedstock are:

1. Steam cracker ethylene product,

2. FCC off-gas,
3. Vents from polyethylene units.

Polymer grade ethylene is the cleanest ethylene feedstock available for OCT. It requires
minimal pretreatment for trace components such as carbon dioxide while other sources of
ethylene typically require more rigorous pretreatment. Though polymer grade ethylene
costs more than other types, capital expenditure is lower because no investment is
required for recovery and purification.

FCC off-gas is an inexpensive source of ethylene since this stream is usually valued at
fuel gas cost. Pretreatment, fractionation and refrigeration are necessary for recovery of
the ethylene product; however, an FCC off-gas recovery system typically has an
attractive internal rate of return.

Another source of ethylene is the high and low-pressure polyethylene unit vents. This
source may not normally provide the quantity of ethylene necessary; consequently, other
sources of ethylene would supplement any shortfall. These vents must be treated to
remove water and oxygen. A compressor is usually required to boost these streams to a
reasonable processing pressure.

Isobutylene Conversion to Normal Butenes

With MTBE phase-out, alternative isobutylene uses will be necessary. For the
production of propylene with the OCT process, isobutylene reacts with itself and normal
butenes to produce isoamylenes and some ethylene and propylene. While isobutylene
does react with n-butenes to produce some propylene, overall propylene production
decreases since isobutylene’s reaction with n-butenes significantly reduces the n-butenes
available to react with ethylene to produce propylene. To enhance the production of
propylene, it is necessary to convert the isobutylene to n-butenes.

CH3 CH2=CH—CH2—CH3
| 1-Butene
CH2=C—CH3 Ù
Isobutylene CH3--CH=CH—CH3
2-Butene
ISOMPLUS technology is a skeletal isomerization process originally developed by
Lyondell Petrochemicals Company to enhance MTBE production by converting normal
butenes to isobutylene. In 1993, Lyondell and CDTECH, a fifty-fifty partnership
between Lummus and Chemical Research and Licensing (CR&L), entered into an
agreement to jointly develop and license ISOMPLUS technology for skeletal
isomerization of C4 and C5 olefins. The process reaction is equilibrium limited and can
be operated to convert isobutylene to normal butenes. Conversion of isobutylene to n-
butenes is approximately 62% with selectivity to n-butenes of approximately 90%.

Figure 2 depicts the flow scheme for the ISOMPLUS process. Isobutylene rich feed is
totally vaporized and superheated prior to entering the fixed bed isomerization reactor where
isobutylene is converted to near-equilibrium yield of n-butenes. The isomerization
reaction is slightly exothermic. Product from the reactor is cooled and sent to a heavies
column for removal of C5 and heavier by-products. These heavy compounds have good
octane value and can be blended into the gasoline pool. The overhead of the heavies
column can be processed in a butene splitter for separation of the unreacted isobutylene.

Figure 2 - ISOMPLUS® Technology

Isobutylene Normal Butenes

Normal
Skeletal Heavies
Isobutylene Butene
Preheat Isomerization Removal
Reactor Product

Gasoline
Product

ISOMPLUS technology has been commercially demonstrated at the Equistar facility in

Channelview, TX with a unit capacity of 10,000 BPD of C4 feed. Lukoil–Perm and Bayer
Rubber Inc. chose ISOMPLUS technology for C4 skeletal isomerization.

Hydroisomerization of 1-Butene to 2-Butene

While it is possible to feed a mixed olefin stream to the ISOMPLUS unit, there are
advantages to increasing the concentration of isobutylene in the feed by removing normal
C4 olefins.

1. The reaction is equilibrium limited; therefore, reducing the normal C4 olefins in the
feed increases the conversion of isobutylene.
2. The size and ultimately the cost of the ISOMPLUS unit are reduced since the capital
and operating costs directly correlate to the gross throughput of the unit.

Catalytic Distillation (CD) combines fractionation and reaction in a single unit operation.
One commercial application of CDTECH’s CDHydro technology combines
hydroisomerization with distillation. This CD application has unique advantages when
applied at typical operating conditions used for the separation of C4s. These unique
advantages include:

• The production of an isobutylene overhead product with a low 1-butene content;

• The increased production of 2-butene from the isomerization of 1-butene.

Additional 2-butene is separated to the bottom of the CD column as it is created, which

allows the reaction of 1-butene to 2-butene to go beyond the limit of single stage
equilibrium. Figure 3 shows the basic CD column as applied to this application. Mixed
C4s feed the CD column along with effluent from the ISOMPLUS unit. A small amount
of hydrogen is required to promote the isomerization reaction. The catalyst section of the
column contains catalyst enclosed in a proprietary structured distillation packing.
Isobutylene rich overhead product is sent to the ISOMPLUS unit. The bottoms product is
rich in 2-butene and lean in isobutylene making it an ideal feed for the OCT unit. A
small purge of hydrogen and non-condensable by-products formed in the ISOMPLUS
unit is removed overhead.

Figure 3 - CDHydro® Technology

Application: Hydroisomerization 1-Butene 2-Butene
Purge

CW

Isobutylene
Product
Hydrogen
ISOMPLUS Effluent
Mixed C4s

STM

2-Butene
Product
Depending on the butadiene content of the mixed C4 stream, it may be advantageous to
have a fixed bed reactor upstream of the CD column. This reactor serves two purposes
to:

1. Saturate high concentrations of butadiene;

2. Perform bulk hydroisomerization.

Increasing the concentration of 2-butene feeding the CD column reduces the amount
created in the rectification section. 2-butene is a heavy component in the separation of
C4s; consequently, less work is required to separate the C4s.

The initial CDHydro process license was for a butene splitter application at Shell’s
Norco, LA refinery. The unit successfully started up in February of 1994. Unlike
traditional fixed-bed technologies, catalyst fouling is not the primary factor that
determines run length in the CDHydro process since fouling is essentially eliminated.
Fouling is minimized by the following inherent characteristics of the CDHydro process:

• Any heavy fouling material contained in the feed separates down and away from the
catalyst zone;
• Any oligomer material formed is much heavier than the surrounding compounds and
immediately separates from the catalyst zone before fouling polymers have sufficient
time to form; and
• Clean reflux continuously washes heavy compounds from the catalyst.

CDHydro technology has fourteen commercial operating units for various hydrogenation
applications with over 350,000 operating hours. None of these units has had a detectable
loss of catalyst activity.

Integrated Processes For Propylene Production from Isobutylene

Figure 4 is a block flow diagram showing the production of propylene from the
combination of process technologies described above. Mixed C4s, essentially free of
butadiene, are fed to the CDHydro butene splitter to separate isobutylene from normal
butenes. The hydroisomerization of 1-butene to 2-butene results in the production of an
isobutylene rich overhead stream and a bottoms stream rich in 2-butene. The isobutylene
stream is ideal feed for the skeletal isomerization of isobutylene to normal butenes and
the bottoms product is perfect for propylene production via metathesis. Since skeletal
isomerization of isobutylene is equilibrium limited, the effluent from the ISOMPLUS
process is returned to the CDHydro butene splitter. This flow scheme is well suited to
both refinery and steam cracker facilities. As mentioned earlier, ethylene feed can be
provided from an accessible source of high purity ethylene or by recovery from low value
by-product streams.
 Figure 4 - Propylene Production from C4 Olefins

Purge

C4 Olefins
Hydroisomerization Skeletal
Isobutylene Gasoline
Hydrogen with CDHydro Isomerization with
Technology ISOMPLUS Technology

Purges

Propylene Propylene
from
Ethylene
OCT

Gasoline

For the refiner, this process provides the following potential advantages:

• A means to meet lower vapor pressure specifications for the gasoline pool;
• Assistance to off-load the alkylation unit.

On the horizon, refiners will be confronted with requirements for reduced RVP and olefin
content specifications for gasoline. These requirements will force refiners to reduce the
amount of C5s blended into the gasoline pool. C4 olefins could be backed out of the
alkylation unit and C5 olefins substituted, thereby reducing the overall vapor pressure of
the gasoline pool as well as the olefins content.
Conclusion

As mentioned in the introduction, alternative process options for isobutylene are

dependent on many site-specific factors. For certain facilities, propylene production may
offer the following advantages:

• A means for increasing operating margins;

• A solution to problems created by MTBE phase-out;
• An option to meet more restrictive RVP and olefin content specifications.

In many cases, transforming olefins to produce propylene may not be the first opportunity
that comes to mind for isobutylene; however, it is an opportunity that should not be
overlooked.

References

JV Builds World’s Largest Single Train Olefins Plant - Thi Chang - Oil and Gas Journal
– September 20, 1999

Refinery 2000: Increase Propylene Recovery from an FCC Unit – R. M. Venner - 1998
De Witt Petrochemical Review

Olefins Conversion Technology - S. M. Edwards – 1998 ABB Lummus Global 9th

Ethylene Technology Seminar.

Triolefins – Break the Propylene Barrier – E. F. Olszewski – CMAI 1998 World

Petrochemical Conference

Alternate Routes to Enhanced Propylene Production – S. J. Stanley, H. Schmitz, M.M.

Shreehan – 1998 ABB Lummus Global 9th Ethylene Technology Seminar

Ethylene 2000 – A. E. Krumins – 1997 – De Witt Technology Conference