Focus on Profit:

C4 Processing Options to Upgrade Steam Cracker

and FCC Streams
By:

Steven I. Kantorowicz, ABB Lummus Global

[email protected]
Telephone: (65) 9635 9729

Presented at:

2nd Asian Petrochemicals Technology Conference

May 7-8, 2002, Seoul, Korea

INTRODUCTION

The future of our industry will be shaped by product flexibility, low capital investment
and energy efficiency of larger capacity plants. Steam cracker and FCC unit owners
are striving to increase the value of their orphaned C4 streams. ABB Lummus Global
offers a full range of technologies to process these C4 streams into value-added
products. New innovative technologies expand the processing choices, including
ethylene/butene metathesis for propylene production, C4 self-metathesis that
produces ethylene, propylene and hexene-1 and catalytic distillation/hydrogenation
for C4 diene removal and hydroisomerization.
This paper reviews the commercially proven C4 processing technologies in the ABB
Lummus Global portfolio, discusses how they work, their advantages, and the
applications that provide the best fit.

Sources of C4s typically include:

Steam Cracker C4s
FCC Unit C4s
Natural Gas Liquids
The typical C4 stream compositions and flow rates from a 600 kta steam cracker and
a 50,000 BPD FCC Unit are shown in the following Table 1. The compositions are
quite dissimilar, which requires a different processing strategy for each one.

Table 1
wt% of C4 stream
600 kta Steam Cracker

50,000 BPD FCC Unit

Butadiene

50

--

Isobutylene

25

15

n-Butenes

15

37

Butanes

10

48

240,000

360,000

TOTAL, mta

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Products from these C4 feeds can include:

Propylene (via metathesis of butenes with ethylene)

Isobutylene

Hexene-1 (via self-metathesis of butenes)

Raffinate for Alkylation

MTBE (or ETBE)

C4 LPG

Butadiene

Maleic Anhydride

Isobutane
The portfolio of C4 processing steps offered by ABB Lummus Global is:
C4 Processing Step

Technology(s)

Metathesis - C2- + C4-

Olefins Conversion (OCT) (ABB

- C4s

Lummus Global)

Selective Hydrogenation

CDHydro ; BASF

Total Hydrogenation

ABB Lummus Global

Dehydrogenation

CATOFIN; CATADIENE (ABB

Lummus Global)

Etherification

CDMtbe, CDEtbe

MTBE Decomposition - Isobutylene

CDIB

Selective Hydrogenation/Etherification

CDEtherol

Butadiene Extraction

BASF

Skeletal Olefin Isomerization

ISOMPLUS (Lyondell/CDTECH)

Paraffin Isomerization

ABB Lummus Global

Maleic Anhydride

ALMA (ABB Lummus Global/Lonza)

The entire ABB Lummus Global technology portfolio is depicted in Figures 1 and 2.
The entire CDTECH1 technology portfolio is depicted in Figure 3.

CDTECH is a partnership between ABB Lummus Global and Chemical Research and Licensing, a
CRI subsidiary. CDMtbe, CDEtbe, CDEtherol, CDHydro, CDIB and ISOMPLUS are all
processes developed and commercialized by CDTECH.
1

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C4 PROCESSING TECHNOLOGIES
Metathesis Olefins Conversion Technology

The Olefins Conversion Technology (OCT) from ABB Lummus Global reacts nbutenes with ethylene to produce polymer grade propylene. This technology, which
has been in commercial operation since 1985, gives the olefin producer added
flexibility to balance ethylene and propylene production depending on market
conditions.

Two chemical reactions take place in the single fixed-bed reactor (Figure 4):
propylene is formed by the metathesis of ethylene and butene-2; and butene-1 is
isomerized to butene-2 as butene-2 is consumed in the metathesis reaction.

This technology can be used with a variety of C4 streams including the mixed C4s
produced in steam cracking, raffinate C4s from MTBE or butadiene extraction, and
C4s produced in FCC units. The ethylene stream can vary from dilute ethylene
typical from an FCC, to polymer-grade ethylene.

All paraffins in the feed pass

through the system as inerts. This feed flexibility allows the producer to take
advantage of many lower-valued feed stocks.

Figure 5 is a simple process flow diagram of the Lummus OCT process. Fresh C4s
plus C4 recycle are mixed with ethylene and sent through a guard bed to remove
trace impurities from the mixed feed. The feed is heated prior to entering the vapor
phase reactor where equilibrium reaction takes place. The per-pass conversion of
butylene is greater than 60% with overall selectivity to propylene exceeding 90%.
The reactor is regenerated on a regular basis.

Reactor effluent is sent to the ethylene recovery tower where unreacted ethylene is
recovered and recycled to the reactor. The C2 tower bottoms are processed in the
C3 tower to produce propylene product and a C4 recycle stream. Purge streams
remove non-reactive light material and C4s and heavier materials.

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In their November 30, 2001 Monomers Market Report, Chemical Market Associates,
Inc. (CMAI) evaluated the relative capital investment required to produce propylene
from various technologies. They range from the capital-intensive route of FCC units
and steam crackers to the low cost of a propylene/propane splitter. As shown in
Figure 6, metathesis is the lowest capital cost route to produce propylene.

The OCT from ABB Lummus Global can also be utilized in butenes self-metathesis
mode to produce ethylene, propylene and hexene-1. This does not use ethylene as
feed to the reactor system. A semi-works self-metathesis unit is under construction
at Sinopecs Tianjin ethylene plant, and will be started up in early 2003.

Selective Hydrogenation

ABB Lummus Global offers two selective hydrogenation processes that can be used
to convert butadiene to normal butenes. The choice depends on project-specific
parameters such as butadiene content, and whether the project is a retrofit or a
grassroots design.
CDHydro Process
This is a technology developed by CDTECH in which hydrogenation and
distillation take place in single unit operation. It has various applications for C3,
C4 and C5 processing.

Applications for C4s include feeds with high or low

butadiene concentration, and involve debutanizer and butene splitter designs.

Catalytic distillation has several inherent advantages over conventional fixed bed
processes:

1. By incorporating hydrogenation in the distillation column, all of the equipment

normally associated with a fixed-bed Selective Hydrogenation Unit is
eliminated. This results in lower capital cost.

2. The catalyst operates at essentially constant temperature in a turbulent flow

regime. This leads to higher selectivity and improved product yields.

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3. Mercaptan compounds react with diolefins, forming heavy olefinic sulfides that
exit in the bottoms. The distillate is sulfur-free.

4. The heat of reaction is used to displace a portion of the reboiler duty. This
reduces energy costs.

5. Dimers, gums and sulfides are much heavier than the surrounding
components. These materials are easily separated down and away from the
catalyst zone. In addition, clean reflux flows over the catalyst zone washing
the catalyst beds. These characteristics lead to more stable operation and
improved catalyst life.
BASF Selop
This is a fixed bed technology developed for steam cracker C4 feeds with high
butadiene concentration.

Process conditions are mild, and all equipment is

constructed of carbon steel.

It was originally commercialized by BASF in

Antwerp in 1993.

In the Selective Hydrogenation Unit, butadiene in the C4 feed stream is

hydrogenated to butenes. By appropriate choice of the process conditions and
catalyst, a C4 effluent with maximum butene-1 or maximum butene-2 can be
achieved. The extent of reaction is such that the treated C4 stream exiting the unit
contains a butadiene level of 10 ppmw. Yield loss to n-butane will vary with the
residual butadiene content and is low.

Selective hydrogenation to achieve a low residual level of butadiene is performed

in a two-stage reactor system.

The reactor feed temperature and butadiene

concentrations are controlled by a recycle of the product from the reactors.

Hydrogen is fed to the reaction loop under flow control.

Optimization of the

hydrogen flow is achieved by setting the hydrogen feed rate proportional to the C4

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feed flow and correcting for the changes in the butadiene content in both the C4
feed and the reactor outlet streams.

Total C4 Hydrogenation
ABB Lummus Global offers its own fixed bed hydrogenation technology for total
saturation of steam cracker C4s for pyrolysis feed, LPG, or n-butane feed
applications.

This well-proven technology offers a unique system for self-balancing reaction heat
removal and a low recycle rate. Changes in heat release due to changes in feed
composition or flow rate cause a corresponding change in vapor generated. Since
condensed vapors are totally recycled, the system adjusts to the new conditions by
automatically changing the recycle quantity.

This design approach results in lower catalyst requirement, long cycle times between
regeneration, and a catalyst life of 5 years or longer.

Butane Dehydrogenation
ABB Lummus Global is the licensor of CATOFIN and CATADIENE technologies.
CATOFIN converts isobutane to isobutylene while CATADIENE converts n-butane to
butadiene. These mature technologies have been utilized in industry for decades,
with improvements being made continuously.

Eight CATOFIN process units are

providing isobutylene feedstock for production of 110,000 BPSD of MTBE.

Single train capability of up to 900,000 MTA of isobutylene affords the producer

lower investment economy of scale, low operating costs, and an environmentally
sound design. Figure 9 is a flow sheet for isobutylene production.

The CATOFIN process uses fixed-bed reactors with a catalyst that has been
selected to optimize the complex relationship among conversion, selectivity and
energy consumption.

The overall selectivity of isobutane to isobutylene via the

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CATOFIN process is greater than 90%. The entire reactor sequence is computer
controlled and requires no operator input. On-stream efficiencies of 98+%, excluding
biannual turnarounds of 2-3 weeks, are routinely achieved.

CATOFIN dehydrogenation is a continuous process, with cyclic reactor operation.

During the hydrocarbon processing step, fresh feed and recycle feed (from an MTBE
synthesis unit or C3 splitter bottoms) are vaporized by exchange with various process
streams and then raised to reaction temperature in the charge heater. The reactor
effluent is routed through a high-pressure steam generator, feed-effluent exchanger,
and trim cooler to the compressor.

The compressor discharge is cooled, dried and routed to the low temperature
recovery section to reject light ends. The low temperature section off-gas, which is a
hydrogen-rich gas, can be sent to a Pressure Swing Adsorption (PSA) Unit to purify
the hydrogen. Recovered liquids from the low temperature recovery section, along
with the effluent flash drum liquid, are fed to distillation facilities and/or an MTBE
synthesis unit for product recovery.

Etherification
The CDMtbe and CDEtbe (Figure 10) technologies licensed by CDTECH convert
isobutylene to MTBE and ETBE using methanol and ethanol respectively. These
catalytic distillation processes have design options for 99.9% conversion. CDTECH
etherification technology continues to capture the majority of projects for these
products.

The patented CDMtbe process is based on a two-step reactor design, consisting of a

boiling point fixed bed reactor followed by final conversion in a catalytic distillation
column. The process utilizes an acidic ion exchange resin catalyst in both its fixed
bed and proprietary catalytic distillation structures.

The unique catalytic distillation column combines reaction and fractionation in a

single unit operation. Conversion of isobutylene in excess of fixed bed equilibrium

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limitations is achieved simply and economically. By using distillation to separate the

product from the reactants, the equilibrium limitation is eliminated and higher
conversion of isobutylene is attained. Catalytic distillation also takes advantage of
the improved kinetics through increased temperature without penalizing equilibrium
conversion.

In September 2001, CDTECH and Snamprogetti announced a global agreement to

combine and market their expertise in the conversion of MTBE units to isooctene/iso-octane production. This is in response to Owners who want to exit the
MTBE market in response to the potential elimination of MTBE from gasoline pools.

MTBE Decomposition

Isobutylene purity in excess of 99.9% can be produced from MTBE using the
CDTECH CDIB technology (Figure 11). This fixed bed process uses a proprietary
acidic catalyst to decompose commercial grade MTBE feed to high purity
isobutylene and commercial grade methanol.

The decomposition reaction takes

place in the vapor phase.

Commercial MTBE feedstock is first fractionated to remove light ends and heavies.
The high purity MTBE is fed to the decomposition reactor where MTBE is converted
to isobutylene and methanol.
steam.

Heat of reaction is supplied by medium pressure

Methanol is extracted from the reactor effluent in a water wash.

Fractionation of the aqueous stream recovers wash water, MTBE for recycle and
methanol.

The water-washed reactor effluent is fractionated to remove heavies

(including MTBE for recycle) and light ends, leaving high purity isobutylene product.

The CDIB technology can be provided as a stand-alone unit or coupled with a

CDMtbe unit to provide an efficiently integrated unit.
operated in several plants worldwide.

-8-

This technology is being

Selective Hydrogenation/Etherification
CDEtherol technology offered by CDTECH processes C4 streams from refinery
units to produce MTBE. The technology, can accomplish selective hydrogenation of
low butadiene
isomerization.

concentration

streams,

etherification,

and

butene-1/butene-2

This technology offers economies in production of ethers and in

alkylation, as well as improved alkylate quality from the isomerization of butene-1 to

butene-2.

This patented process is based on a two-step reactor design, consisting of an

ETHEROL trifunctional catalyst reactor followed by final conversion in a catalytic
distillation column. The process utilizes a proprietary trifunctional catalyst in its fixed
bed reactor and acidic ion exchange catalyst in its proprietary catalytic distillation
structures.

Butadiene Extraction

BASFs butadiene extraction process uses non-corrosive n-methyl pyrrolidone

(NMP) as the extractive distillation solvent. The unit is comprised of the following
sections: Extractive Distillation; Degassing; Distillation; Solvent Regeneration;
Chemical Injection System and Waste Water Stripping.

The evaporated crude C4 stream enters the first column, the main-washer, at the
bottom of the tower.

NMP, in a counter-current flow, washes the more soluble

butadiene and the acetylenes out of the C4-cut. This solution is pumped to the top of
the rectifier. The acetylenes are removed in the after-washer column, where they
are dissolved in NMP at the bottom. The top product of the after-washer is the crude
butadiene. This stream will finally be distilled to meet product specifications.

This mature technology offers advantages in feedstock flexibility, energy efficiency,

safety, and simplified plant operations.

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C4 Olefin Skeletal Isomerization

CDTECH and Lyondell Petrochemical Co, offers the ISOMPLUS fixed bed skeletal
olefin isomerization technology (Figure 12) for conversion of n-butenes into
isobutylene.

A zeolite catalyst specifically developed for this service provides near-equilibrium

conversion of normal butenes to isobutylene at high selectivity and long process run
lengths. A simple process scheme results in low capital and operating costs.

Hydrocarbon feed containing normal butenes, such as MTBE unit raffinate, is

evaporated and superheated prior to entering the skeletal isomerization reactor. The
hydrocarbon stream does not require steam or other diluents, or the addition of
catalyst activation agents to promote the reaction. The hot vapor passes through a
fixed bed reactor where up to 44% of the contained normal butenes are converted to
isobutylene at approximately 90% selectivity.

Reactor effluent is cooled and

compressed to a heavy end column where C5+ is separated by fractionation.

The butene Isomerate is suitable for feed to an MTBE unit. When an ISOMPLUS
unit is operated in a recycle mode with a high conversion MTBE unit, production of
MTBE can be significantly increased.

Paraffin Isomerization

ABB Lummus Global offers its own isomerization technology for efficient conversion
of n-butane to isobutane. A main application is in field butane-based MTBE plants
where isobutane is produced as feedstock for the dehydrogenation unit.

The

technology is also used in refineries to produce isobutane feedstock for alkylation

units.

The process technology combines high per-pass conversion and selectivity to

achieve high product yields (ca. 98.5 wt% on a C4 basis). High catalyst activity and
stability at low hydrogen flow rates minimize required reactor volumes and can allow

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the elimination of hydrogen recycle facilities. Capital cost is further minimized by

including commercially proven proprietary fractionation hardware to reduce the size
of the deisobutanizer product recovery tower.

This process, which utilizes an AKZO/TOTAL catalyst, has been utilized in many
projects representing more than two million MTA of isobutane production. The first
plant came on stream in 1995 as part of an ABB technology package of
ISOM/CATOFIN/CDMtbe to produce MTBE.

Maleic Anhydride - ALMA

The ALMA process produces high purity, superior quality maleic anhydride from nbutane. Jointly developed and licensed by ABB and Lonza SpA, the ALMA process
combines the unique features of a fluid-bed reactor with that of a non-aqueous
recovery system. This modern processing combination results in savings in capital
investment and a product that surpasses the rigorous performance specifications of
various end-use markets.

The exothermic heat of reaction is removed by generating saturated high pressure

steam, which is combined with the steam produced in the off-gas incinerator and
superheated. A portion of the steam can be used to drive the air compressor, with
excess exported or used to generate electric power. This results in greater energy
efficiency for the process.

C4s PROCESSING OPTIONS

Steam Cracker C4s Processing Options
Steam crackers have the greatest number of C4 processing options due to several
factors:
The high butadiene content in the crude C4s
The option of saturating the C4s and recycling to pyrolysis, and

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 The availability of ethylene for metathesis with mixed n-butenes or butene-2 to

produce propylene
Self-metathesis for ethylene, propylene and comonomer hexene-1
As seen in Figure 14, crude C4s from a cracker can be treated in many ways. The
most attractive C4 processing alternative is ABB Lummus Globals Olefins
Conversion Technology (OCT) that converts ethylene plus butene-2 or mixed nbutenes to produce propylene. OCT combined with a steam cracker can significantly
vary the propylene-to-ethylene product ratio and improve overall plant economics.

Typical steam crackers with liquid feedstocks operate with a propylene-to-ethylene

ratio range of 0.45 to 0.65 depending upon cracking severity. The mixed C4 product
stream contains butadiene, butylenes and butanes. Butylenes can be reacted with
ethylene via metathesis to increase the propylene-to-ethylene ratio. If butadiene is
not required as a product, it can be selectively hydrogenated to butenes to provide
additional butylene feed for metathesis. The steam cracker/OCT combination can
result in propylene-to-ethylene ratios exceeding 1.1 as determined by the quantity of
butylenes that are available for conversion in the OCT unit (Figure 15).

The BASF Fina Petrochemicals steam cracker in Port Arthur, Texas produces over
950,000 metric tons per annum (MTA) ethylene and over 544,000 MTA propylene.
An OCT unit is under construction that will add more than 300,000 MTA additional
propylene, increasing the propylene-to-ethylene ratio (P/E) from 0.57 to 1.0.

The ethylene-butene metathesis is also being used by Shanghai SECCO

Petrochemical, the joint venture of BP (50%), Sinopec (30%) and Sinopec Shanghai
Petrochemical (20%), which is building a 900,000 MTA ethylene plant at Caojing,
China. The overall P/E ratio is 0.65,as some butadiene is recovered as product.

Table 2 illustrates three operating scenarios. Case 1 recovers C4s as a mixed C4

product. This is typical of an operation where butadiene is a desired product for
recovery. Case 2 hydrogenates and recycles the C4s to cracking. The naphtha feed
requirement is reduced. This operating scenario has become more popular in recent
years as butadiene demand has not kept pace with ethylene growth rates. However,
- 12 -

this option reduces the quantity of hydrogen available for product sales. A more
economic variation of Case 2 is to selectively hydrogenate the butadiene to
butylenes to produce metathesis feed. This is shown in Case 3. The
propylene/ethylene product ratio increases from 0.55 for Cases 1 and 2 to 0.94 for
Case 3. This option requires more naphtha feed but 73% of the incremental naphtha
feed is converted to propylene via metathesis. The IRR improves by 3 5%
depending upon product price scenarios.

Table 2

Material Balance Comparison

Case
Case Description

1
Stand-alone
Steam Cracker
Exported C 4s

Stand-alone
Steam Cracker
No Exported C 4s

Steam Cracker
integrated with
an OCT Unit

Feedstock, kta
Naphtha Feed

2088

1810

2213

Methane Fuel Gas

389

393

437

PG Ethylene

760

760

760

PG Propylene

418

418

713

Mixed C 4s

263

Pygas

196

181

235

60

56

66

2088

1810

2213

+403*

Products, kta

Fuel Oil
Acid Gas
Total

+295*

* 73% of incremental naphtha converted to propylene

In addition to maximizing the propylene-to-ethylene (P/E) ratio of a steam cracker,

OCT can also be utilized to optimize steam cracker complexes operating in the
conventional P/E range.

Table 3 illustrates different naphtha steam cracker options that produce an overall
P/E ratio of 0.65. In Case 4, the P/E ratio is controlled by the cracking severity; the
0.65 P/E ratio represents a typical low severity operation on naphtha feed. In Case 5,
the severity is increased and the OCT unit is added to react butylenes and ethylene
to attain the same 0.65 ratio. A range of values are shown in Case 5 to reflect the

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results depending upon whether butadiene is recovered as product or selectively

hydrogenated to produce more OCT unit feed. Addition of the OCT unit results in a
lower cost complex with lower specific energy consumption that in turn results in
improved gross and net margins for the steam cracker/OCT combination.

Table 3
Feedstock
Naphtha Severity
P/E
Naphtha Feedrate
C3- from OCT
TIC
Gross Margin
Net Margin
Energy
BD
Benzene
Pygas

Case 4
Naphtha
Low
0.65
Base
-Base
Base
Base
Base
Base
Base
Base

Case 5
Naphtha
High
0.65
2 - 5% lower
15 - 28%
5 - 8% reduction
<1 - 3% improvement
2 - 6% improvement
8 - 9% lower
17% less
25 - 50% more
<2 - 12% less

Since the OCT unit produces propylene, the steam cracker can operate at higher
cracking severity while maintaining the same overall P/E ratio. The higher cracking
severity processes less feed and produces less by-products, resulting in a smaller
ethylene plant. Since the ethylene plant is the major cost and energy component, the
overall result is that the steam cracker/OCT unit combination outperforms the low
severity steam cracker. The addition of the OCT unit to the steam cracker improves
capital and operating expenses as compared to larger plants operating in the
traditional low severity range.

In addition to the advantages discussed for grassroots complexes, the OCT unit can
also be used as an effective debottlenecking tool. It can be applied to plants
currently operating at low severity and looking to increase capacity without sacrificing
P/E ratio or for plants operating at high severity and looking to debottleneck for
higher capacities and P/E ratios.

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The crude C4s can be totally hydrogenated to C4 LPG using ABB Lummus Global
technology.

BASF Butadiene Extraction can produce butadiene for those

applications where there is an attractive market.

BASF selective hydrogenation technology can be used to convert butadiene to

normal butenes. CDMtbe or CDEtbe can be used for etherification. Alternatively,
CDEtherol can generally be used in lieu of separate selective hydrogenation and
etherification steps to process raffinates from butadiene extraction.

To enhance MTBE or ETBE production, ISOMPLUS technology can be used.

If pure isobutylene is required, CDIB MTBE cracking technology can be used.

FCC C4s Processing Options

In current market conditions, FCC unit profitability is significantly enhanced by the
increased flexibility to operate at higher propylene production rates and recoveries.
It is currently feasible to double or triple FCC propylene yields by utilizing
combinations of customized catalysts, higher severity operation, enhanced FCC
design features and improved recovery facilities.

Selective Component Cracking (SCC) is Lummus maximum olefins catalytic

cracking process. In this high olefin production mode the yield of gasoline decreases
but the octane number increases. As the yield of propylene increases, the ethylene
yield also increases. Ethylene recovery followed by butylene/ethylene metathesis to
propylene can improve overall FCC plant economics (Figure 16).

ABB Lummus Global has a patented low cost low-pressure-recovery (LPR) flow
scheme for ethylene recovery in cat cracking units that does not sacrifice reliability,
flexibility or safety. In this process, typically greater than 95% of the ethylene is
recovered from the FCC off gas stream that is normally used as fuel gas.

Adding the LPR unit results in simple payouts typically less than two years, with
excellent returns over the historical range of ethylene prices. LPR upgrades ethylene
- 15 -

in FCC offgas from fuel value to product value. Most refineries with operating FCCs
have the infrastructure in place for handling propylene product but not ethylene
product. So the LPR process can also be used to recover ethylene for further
processing via metathesis with refinery C4s to maximize propylene. The LPR/OCT
combination further improves the economics over the LPR unit alone.

The Figure below illustrates the IRR over a range of product values for ethylene
recovery only and propylene production via LPR/OCT. Adding the OCT to the LPR
unit increases IRR 10 to 20% even after considering that historically propylene price
ranges 0.8 to 0.85 of ethylene price. This is because the major feed in producing
propylene is butylene, which is significantly lower in price than either ethylene or
propylene. The OCT unit combined with FCC maximizes high propylene production
flexibility.

Refinery Offgas Olefin Recovery Effect of

Propylene and Ethylene Prices on IRR
Increasing IRR
Propylene Production from
Offgas via an OCT unit

Propylene
Ethylene
Ethylene Recovery from
Refinery Offgas. No OCT unit

300

350

400

450

500

550

600

650

Ethylene or Propylene Price $/MT

Typical FCC processing options are depicted in Figure 17.

If ethylene is not

recovered, C4 self-metathesis can produce propylene and comonomer hexene-1.

FCC C4s can be processed to MTBE plus butadiene-free raffinate for alkylation.
MTBE production can be enhanced by skeletal isomerization of normal butylenes.
Butene-1 can be produced from normal butylenes.

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CDHydro technology is used to selectively hydrogenate butadiene in the C4 feed to

normal butenes. CDMtbe or CDEtbe etherification technology produces MTBE or
ETBE. Alternatively, CDEtherol can be used to accomplish selective hydrogenation
and etherification within a single process unit (dashed box).

ISOMPLUS technology can greatly increase MTBE production beyond the amount
based on the isobutylene content of the FCC C4s.
ALMA maleic anhydride technology offers an additional option to produce these high
value-added products.

Natural Gas Liquids Processing Options

Saturated C4s from natural gas liquids can be processed into isobutane, isobutylene,
MTBE (or ETBE), or butadiene, as depicted in Figure 18.

Using the paraffin isomerization technology from ABB Lummus Global, C4 LPG or nbutane can be isomerized to isobutane. Isobutane is dehydrogenated to isobutylene
using CATOFIN technology. The isobutylene can be etherified with methanol or
ethanol using CD Mtbe or CDEtbe technology to supply the markets for MTBE and
ETBE. In situations where butadiene shortfall exists, CATADIENE can be used to
produce butadiene.

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SUMMARY

Product flexibility, low capital investment and energy efficiency of larger capacity
plants will shape the future of the olefins industry. The choice of C4 processing
technology requires optimization for the individual site requirements to maximize
return on investment.

The ABB Lummus Global C4 processing portfolio offers a full range of

commercialized technologies for upgrading of low value C4 streams from Steam
Crackers, FCC Units and Natural Gas Liquids to produce propylene, butene-1,
butadiene, isobutylene, MTBE and hexene-1. We have built this broad base of
processes through research and development, co-venturing process development
and executing license agreements with industry leaders.

For further information please contact us on ABB Lummus Globals website at

www.abb.com/lummus.

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REFERENCES
Lummus Claims Recovery Package Cuts Costs, Raises Coproduct Value
Chemical Week February 27, 2002
Stephen J. Stanley, interviewed by Andrew Wood Chemical Week
Capital Investment for Propylene Production
CMAI November 2001
Metathesis: Refinery and Ethylene Plant Applications
The 1st Asian Petrochemicals Technology Conference, Taipei, May 22-23, 2001
Steven I. Kantorowicz and Ronald M. Venner ABB Lummus Global
Innovative Technologies for Capacity Expansion and Product
Flexibility of Steam Crackers
The 11th Ethylene Conference, Maoming, PRC November 20-23,2000
Steven I. Kantorowicz ABB Lummus Global
JV Builds Worlds Largest Single Train Olefins Plant
Oil & Gas Journal September 20, 1999
Thi Chang Oil & Gas Journal
Low Pressure Recovery of Olefins from Refinery Offgases
Lummus 8th Ethylene Seminar
Frank D. McCarthy and Aivars E. Krumins
Olefins Conversion Technology
Lummus 9th Ethylene Technology Seminar
S.M. Edwards
Propylene Options
EEPC HSE Conference 2000
Aivars E. Krumins
Ethylene
Kirk-Othmer Encyclopedia of Chemical Technology 4th Edition
K.M. Sundaram, E.F. Olszewski and M.M. Shreehan

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Figure 1

ABB Lummus Global Technology Portfolio

Chemical/Petrochemical/Polymer Processes
Ethane

Polyethylene

LPG

Olefins

Naphtha

Ethylene

Ethylbenzene

AGO/VGO

OCT

C6-C8s
C4s

Benzene

Butanes

Propane
Dehydrogenation

Polystyrene
Expandable
Polystyrene

Polypropylene

Propylene

Hydrodealkylation

Propane

Styrene

Cumene

Phenol

Butadiene
Extraction

MTBE

Propylene

Isomerization

Butane
Dehydrogenation

Maleic
Anhydride

Aromatics
Saturation

- 20 -

Isobutylene

Bisphenol- A

Figure 2

ABB Lummus Global Technology Portfolio

Refining Processes
Sat. Gas
Plant
C5/C6

Crude
Unit

C5/C6 Isom.

Methanol
Ethanol

Hydrogen
Plant

Butane
Isomerization

Ethylene Plant C4s

SynSat/
SynShift/
SynFlow

Unsat
Gas Plant

Hydrogenation

(R)FCC

FCC Gasoline
HDS

Ethylene
Plant Feed
Vacuum
Unit

Hydrocracking

RDS
Thermal Gasoil
Conversion

MTBE
ETBE

Isomerate

Naphtha
Middle Distillates

Butane
Dehydrogenation

Naphtha
Jet
Diesel

Visbreaking &
Deep Thermal
Conversion

Isodewaxing

Fuel Oil from

Ethylene Plant

LC-FiningSM

Delayed Coker

Chevron Lummus Global

CDTECH
*with OCR and UFR technologies

- 21 -

TAME
TAEE

Methanol
Ethanol

Needle Coker

VRDS*

ISOMPLUS

Hydrofinishing

Figure 3

CDTECH Technology Portfolio

Hydrogenation

Etherification
---MTBE
---TAME
---ETBE
---TAEE
---BTBE

---Acetylenes
---Diolefins
---Aromatics
---Olefin Isomerization
---Olefin Saturation
---AMS

Alkylation

Hydrodesulfurization
---LSR Naphtha
---Reformer Feed
---Kerosene
---Diesel
---FCC Gasoline

---Ethylbenzene
---Cumene

Other

---Sulfur reduction
---Mercaptan reduction
---Acrylamide

- 22 -

---Iso-octene
---Iso-octane

Figure 4

Olefins Conversion Technology (OCT)

Propylene from ethylene and butene

Ethylene + 2-Butene
1-Butene

2Propylene
2-Butene

Ethylene
Pretreatment

Preheat

Reactor

Butylene

Ethylene/Butylene
Recycle
Unreacted
C2 & C4

Product
Fractionation
Gasoline
Propylene Product

Low capital route

to propylene
- 23 -

Figure 5

OCT - Process Flow Schematic

Guard Bed

Metathesis Reactor

Ethylene Column

Propylene Column

Recycle Ethylene

Lights Purge

Ethylene Feed
Propylene Product

C4 Feed

C4 Recycle

No Superfractionators Required
- 24 -

Figure 6

Relative Capital Investment for Propylene Production

Investment
US$ Per Annual Ton

2500

2000

1500

1000

500

0
FCC

Naphtha
Steam Cracker

FCC +
ZSM-5

Propane Dehyro

Investment per annual ton propylene

Ref: CMAI Nov. 30, 2001

- 25 -

Metathesis

Splitter

Figure 7

CDHydro Tower
Hydrogen Vent

Reflux + Heat of Rx
Hydrogen
Tower
Feed

Net Overhead
Catalyst
Zone

Net Bottoms

- 26 -

Figure 8

Total C4 Hydrogenation
Reactor

Stabilizer
MP
Steam
Offgas
CW
Offgas

LP
Steam

CW

H2
CW

C4 feed

C4 LPG

- 27 -

Figure 9

CATOFIN Dehydrogenation Processing Scheme

CHARGE HEATER
AIR HEATER

REACTOR ON
PURGE

REACTOR ON
STREAM

AIR

REACTOR ON
REHEAT
FUEL
EXHAUST AIR

STEAM
STEAM
ISOBUTANE

C4 RECYCLE
FROM MTBE
SYNTHESIS

FUEL GAS

LOW TEMP.
SECTION
COOLER

DEPROPANIZER
COOLER

FLASH DRUM
PRODUCT
COMPRESSOR

ISOBUTYLENE TO
MTBE SYNTHESIS

- 28 -

Figure 10

CDTECH Ethers Process

MTBE or ETBE
Primary
Reactor

Catalytic
Distillation
Tower

Methanol/Ethanol Methanol/Ethanol
Extraction
Recovery

C4 Recycle to
Dehydrogenation
Unit

Methanol/Ethanol

C4s Methanol/Ethanol

Water

Mixed C4s from

Dehydrogenation
Unit

MTBE/ETBE Product

- 29 -

Figure 11

CDTECH - CDIB
Isobutylene Unit Integrated With MTBE Unit
MTBE
Topping
Column

MTBE
Tailing
Column

Isobutylene
Reactors

Crude
Isobutylene
Column

Methanol
Extraction
Column

Isobutylene
Lights
Column
C4's/C5's

Water From MTBE Unit

Lights

MTBE Feed

Isobutylene
Methanol/Water To MTBE Unit
MTBE/Methanol To MTBE Unit
Heavies

- 30 -

Figure 12

ISOMPLUS
C4 Skeletal Isomerization Process

Heater

Compressor
Heavy Ends
Column

Reactor

MTBE Raffinate

C5 +

- 31 -

Figure 13

Maleic Anhydride
HP Steam
Tail Gas*
Steam
Drum

Light
Ends
Column

Pure Maleic
Anhydride

Catalyst
Fines
Recovery

Product
Column

Absorber

n-butane

Light Ends*

Fluid
Bed
Reactor

Stripper

Air
Solvent
Purification

- 32 -

Aqueous Effluent

Figure 14

Steam Cracker Ethylene & C4s Processing Scheme

Butadiene

Butadiene
Extraction
Steam
Cracker
C4s

Raffinate 1

Selective
C4 Hydro
Reactor 1

Selective
C4 Hydro
Reactor 2

~
Hydrogen

~
Hydrogen

Total
Hydrogenation

Hydrogen

DIB

Propylene

OCT

Raffinate 2

MTBE

Ethylene

~
MTBE

C4 LPG or
Recycle
to Ethylene Plant
Heaters

OSBL or
Recycle to
Ethylene Plant
C4+ Purge
Heaters

Isobutene,
Isobutane &
1-Butene

Butene-1
Recovery

- 33 -

MTBE
Decomposition

Butene-1

Isobutylene

Figure 15

Steam cracker OCT results

High
Severity

Low
Severity

1.2
1
0.8
C3-/C20.6
Ratio
0.4
0.2
0
Max C2-

+OCT

Max C3-

+OCT

OCT enhances P/E product flexibility for all crackers

- 34 -

Figure 16

FCC Propylene
OCT Results
30

25

Propylene
Yield
Wt%

20

15

10

0
FCC

FCC ++

- 35 -

SCC

+ OCT

Figure 17

FCC C4s & FCC Off Gas Processing Scheme

MTBE

Butene-1
Recovery
Butene-2
FCC
C4s

Selective
C4 Hydro
Reactor 1

MTBE

OSBL or
Recycle to
Ethylene
Plant Heaters

Butene-1

Selective
C4 Hydro
Reactor 2

C4+ Purge
OCT

Propylene

Skeletal
Olefin
Isomerization

FCC
Offgas

Contaminant
Removal

Low
Pressure
Recovery

Ethylene
Fuel Gas
C3+ to OSBL
or Recovery
in OCU

- 36 -

Figure 18

Natural Gas Liquids Processing Scheme

Isobutane
Methanol

C4 LPG

Paraffin
Isomerization

Dehydrogenation
(CATOFIN)

MTBE

Etherification

Isobutane

n-Butane

Dehydrogenation
(CATADIENE)

- 37 -

Butadiene