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278 SEGMENT 3. PETROCHEMICAL PROCESSES

BTX aromatics BTX aromatics

Application: To produce high yields ofbenzene, toluene, xylenes and Application: An aromatics process based on extractive distillation, GT-
hydrogen from naphthas via the CCR Aromizing process coupled with BTX efficiently recovers benzene, toluene and xylenes from refinery or
RegenC continuous catalyst regeneration technology. Benzene and petrochemical aromatics streams, such as catalytic reformate or pyroly-
toluene cuts are fed directly to an aromatics extraction unit. The xylenes sis gasoline.
fraction, obtained by fractionation and subsequent treatment by the
Arofining process for diolefins and olefins removal, is ideal for paraxy- Description: Hydrocarbon feed is preheated with hot circulating sol-
lene and orthoxylene production. vent and fed at a midpoint into the extractive distillation column (EDC).
Lean solvent is fed at an upper point to selectively extract the aromatics
Description: This process features moving bed reactors and a con- into the column bottoms in a vapor/liqwd distillation operation. Nonaro-
tinuous catalyst regeneration system coupled with a hard, smooth-flow- matic hydrocarbons exit the column top and pass through a condenser.
ing catalyst. Feed enters the reactor (I), passes radially through the mov- A portion of the overhead stream is returned to the column top as reflux
ing catalyst bed, exits at the reactor bottom and proceeds in the same to wash out any entrained solvent. The balance of the overhead stream
manner through the 2-3 remaining reactors (2). The robust (latest gen- is the raffinate product, requiring no further treatment.
eration AR 501 & 505) catalyst moves downward through each reactor. Rich solvent from the bottom of the EDC is routed to the solvent-
Leaving the reactor, the catalyst is gas-lifted to the next reactor‘s feed hop- recovery column (SRC), where the aromatics are stripped overhead. Strip-
per where it is distributed for entry. After the last reactor, an inert gas lift ping steam from a closed-loop water circuit facilitates hydrocarbon strip-
system isolates and transports the catalyst to the recently-introduced ping. The SRC operates under vacuum to reduce the boiling point at the
RegenC regeneration section (3). Coke is removed; catalyst is returned column base.
to its original state and sent to the first reactor; the cyde begins again. A Lean solvent from the bottom of the SRC is passed through heat
recovery system (4) separateshydrogen for use in downstream units and exchange before returning to the EDC. A small portion of the lean cir-
the Aromizate is sent to a stabilizationsection. The unit is l l l y automated culating solvent is processed in a solvent-regeneration step to remove
and operating controls are integrated into a DCS, requiring only a min- heavy decomposition products, which are purged daily.
imum of supervisory and maintenance effort. The process advantages over conventional liquid-liquid extraction
processes indude lower capital and operating costs and simplicity of oper-
Yields: (YO) ation. Advantages over other extractive processes include: superior sol-
Feed Products
TBP cut, “C 80-1 50 Hydrogen 4.1 vent system, fewer equipment pieces, small equipment and expanded
Paraffins 57 c5+ 87 feedstock range. Design flexibility allows use for grassroots aromatics
Naphthenes 37 Benzene 8.5 recovery units or debottleneckingconventionalsystems in many revamp
Aromatics 6 Toluene 26.3 configurations.
Xylenes 26.1
Total aromatics 74.3 Economics:
Expansionof conventional
Economics: The ISBL investment for a typical 25,000-bpsd CCR New unit BTX recovery unit
Aromizing unit with a RegenC regenerator, 2002 Gulf Coast location. Feed, bpd 3,500 Lt. 4,000
reformate incremental
Investment including initial catalyst inventory,* Capital cost, $MM 6.5 3.5
US$ million 52 Simple pretax payout, yr 2.2 1.2
Typical utility requirements: ROI, % 44 85
Fuel, lo6 kcallh 76
Steam, HP tlh (net export) (17)
Commercial plants: Three grassroots applications.
Electricity, kWh/h 5,900 Reference: “Benzene reduction in motor gasoline-obligation or
Catalyst operating cost, $/ton feed 0.5 opportunity,” Hydrocarbon Processing Process Optimization Conference,
* Exclusive of noble metals April 1997. “Improve BTX processing economics,”H9mcmbon Processing,
March 1998.
Commercial plants: Sixty CCR reforming units have been licensed
including seven plants in operation and four under design. Licensor: GTC Technology Inc.
Licensor: Axens, Axens NA.
 SEGMENTS. PETROCHEMICAL PROCESSES 279

BTX aromatics BTX aromatics

Application: To produce petrochemical-grade benzene, toluene and Application: To produce reformate, which is concentrated in benzene,
xylenes (BTX) via the aromatization of propane and butanes using the toluene and xylenes (BTX) from naphtha and condensate feedstocks via
BP-UOP Cyclar process. a high-severity reforming operation with a hydrogen byproduct. The CCR
Platforming Process is licensed by UOI?
Description: The process consists of a reactor section, continuous cat-
alyst regeneration (CCR) section and product-recovery section. Stacked Description: The process consists of a reactor section, continuous cat-
radial-flow reactors (1) facilitate catalyst transfer to and from the CCR alyst regeneration section (CCR) and product recovery section. Stacked
catalyst regeneration section (2). A charge heater and interheaters (3) radial flow reactors (1) facilitate catalyst transfer to and from the CCR
achieve optimum conversion and selectivityfor the endothermic reaction. catalyst regeneration section (2). A charge heater and interheaters (3) are
Reactor effluent is separated into liquid and vapor products (4). The liq- used to achieve optimum conversion and selectivity for the endothermic
uid product is sent to a stripper column ( 5 ) to remove light saturates from reaction.
the Cg- aromatic product. Vapor from the separator is compressed and Reactor effluent is separated into liquid and vapor products (4). Liq-
sent to a gas recovery unit (6). The compressed vapor is then separated uid product is sent to a stabilizer ( 5 ) to remove light ends. Vapor from
into a 95% pure hydrogen coproduct, a fuel-gas stream containing light the separator is compressed and sent to a gas-recoverysection (6) to sep-
byproducts and a recycled stream of unconverted LPG. arate 90%-pure hydrogen byproduct. A he1 gas byproduct of LPG can also
be produced. UOP’s latest R-270 series catalyst maximizes aromatics
Yields: Total aromatics yields as a wt% of fresh feed range from 61% yields.
for propane to 66% for mixed butanes feed. Hydrogen yield is approx-
imately 7-wt% fresh feed. Typical product distribution is 27% benzene, Yields: Typical yields from lean Middle East naphtha:
43% toluene, 22% Cg aromatics and 8% C; aromatics. Hz, wt% 4.3
Economics: US Gulf Coast inside battery limits basis, assuming gas Benzene, wt% 1.7
turbine driver is used for product compressor, Toluene, wt% 29.9
Xylenes, wt% 30.4
Investment, US$ per metric ton (mt) of feed 175-208 Ag+, wt% 13.1
Fypical utility requirements, unit per mt of feed Economics: Capital investment per mtpy of feed:
Electricity, kWh 0.013
Steam, MP, mt (credit) (0.7) US$ 50-75
Steam, LP, mt 0.13 Utilities per metric ton feedrate
Water, cooling, mt 19 Electricity, kWh 12
Fuel, MMkcal 2 Steam, HP, mt 0.16
Boiler feedwater, m t 0.55 Water, cooling m3 20
Commercial plants:In 1990, the first Cyclar unit was commissioned Fuel, MMkcal 0.13
at the BP refinery at Grangemouth, Scotland. This unit was designed to Commercial plants: There are 173 units in operation and 30 addi-
process 1,000 bpd of C3 or C4 feedstock at either high- or low-pressure tional units in design and construction. Total operating capacity repre-
over a wide range of operating conditions. A second unit capable of sents over 3.9 million-bpd.
processing C3 and C4 feedstock was commissioned in 2000, and oper-
ates at design capacities. Licensor: UOP LLC.
Reference: Doolan, I? C., and I? R. Pujado, “Make aromatics from
LPG,” Hydrocarbon Processing, September 1989, pp. 72-76. Gosling, C.
D., et al., “Process LPG to BTX products,” Hydrocarbon Processing
December 1991.
Licensor: UOP LLC.
280 SEGMENT 3. PETROCHEMICAL PROCESSES

Lean solvent
I
+ I L
Leansolvent + I

Butadiene extraction Butanediol, 1,4-

Application: To produce a polymer-grade butadiene product from Application: To produce 1,4 butanediol (BDO) from butane via
mixed-C* streams by extractive distillation using acetonitrile (ACN) as maleic anhydride and hydrogen using ester hydrogenation.
the solvent.
Description: Maleic anhydride is first esterified with methanol in a
Description: This butadiene extraction process was originally devel- reaction column (1) to form the intermediate dimethyl maleate. The
oped by Shell Chemicals. It is offered under license agreement by Kel- methanol and water overhead stream is separated in the methanol col-
logg Brown &Root, who has updated and optimized the process to reduce umn (2) and water discharged.
capital and operating costs. The ester is then fed directly to the low-pressure, vapor-phasehydro-
The process scheme consists of contacting mixed-C4 feed with lean sol- genation system where it vaporized into an excess of hydrogen in the
vent in the extractive distillation column (1). The raGnate, butenes and vaporizer (3) and fed to a fixed-bed reactor (4), containing a copper cat-
butanes, which are not absorbed, flow overhead to the wash column (2) alyst. The reaction product is cooled (5) and condensed (6) with the
for solvent recovery. The butadiene-rich solvent flows to the stripper sys- hydrogen being recycled by the centrifugal circulator (7).
tem (3) where the butadiene is separatedfrom the solvent. Raw butadiene The condensed product flows to the lights column (8) where it is dis-
is purified to meet specifications in the purification section (4). Heavy tilled to produce a small co-product tetrahydrohran (THF) stream. The
ends (Cd acetylenes) are also separated in the stripper system (3) as a side heavies column (9) removes methanol, which is recycled to the methanol
product and further processed in the heavy-ends stripping section (5). column (2). The product column (10) produces high-quality butanediol
The solvent recovery step (6)maintains solvent quality and recovers sol- (BDO). Unreacted ester and gamma butyralactone (GBL) are recycled
vent from various product streams. to the vaporizer (3) to maximize process efficiency.
Use of acetonitrileis advantageous to other solvent systems for a num- The process can be adapted to produce higher quantities of co-prod-
ber of reasons. ACNs lower boiling point results in lower operating tem- uct THF and to extract the GBL as a co-product if required.
peratures resulting in low fouling rates and long run-lengths. Only low-
pressure steam is required for reboilers. The low molecular weight and low Economics:per ton of BDO equivalent
molar volume of ACN, combined with its high selectivity to butadiene, Maleic anhydride 1.125
results in low solvent circulation rates and smaller equipment sizes. The Hydrogen 0.116
low viscosity of ACN increases tower efficiencies and reduces column size Methanol 0.050
and cost. ACN is also very stable, noncorrosive and biodegradable. The Electric power, kWh 164
basic process is noncorrosive and requires only carbon steel materials of Steam, tons 3.6
construction. Water, cooling, m3 326

Yields: This process can exceed 98% recovery of the butadiene contained Commercial plants: Since 1989, six plants have been licensed with
in the feed as product. This product will meet all butadiene derivative a total capacity of 300,000 tpy.
requirements with typical specifications shown below. Licensor: Davy Process Technology, UK.
Component Value Units
1,3-Butadiene 99.5 YOwt. Minimum
Total acetylenes 20 ppmwt maximum
Methyl acetylene 10 ppmwt maximum
Vinyl acetylenes 10 ppmwt maximum
Propadiene 10 ppmwt maximum
1,2-Butadiene 10 ppmwt maximum
C5 hydrocarbons 200 ppmwt maximum
Commercial plants: Over 35 butadiene units have been con-
structed using the Shell ACN technology. Unit capacities range from 20
Mtpy to over 225 Mtpy.
Licensor: Kellogg Brown & Root, Inc.
 SEGMENTS. PETROCHEMICAL PROCESSES 281

Butanediol, 1,4- Butene-I

Application: To produce 1,Cbutanediol (BDO), or mixture of BDO Application: To produce high-purity butene-1 that is suitable for
with tetrahydrofuran (THF) andlor gamma-butyrolactone(GBL) from copolymers in LLDPE production via the Alphabutol ethylene dimer-
normal butane using a fluid-bed oxidation and fuced-bed hydrogenation ization process developed by IFPiAxens in cooperation with SABIC.
reactor combination.
Description:Polymer-grade ethylene is oligomerized in the liquid-phase
Description: BP Chemicals has combined its 40 years of experience reactor (1) with a catalyst system that has high activity and selectivity. Liq-
in fluid-bed oxidation technology with Lurgi Oel-Gas-ChemieGmbHs uid effluent and spent catalyst are then separated (2); the liquid is distilled
30 years of hydrogenation expertise to jointly develop a direct, dual-reac- (3) for recycling of unreacted ethylene to the reactor and fractionated (4)
tor process, called the GEMINOX BDO. into high-purity butene-1.Spent catalyst is treated to remove volatile hydro-
Air and n-butane are introduced into a fluid-bed, catalytic reactor carbons and recovered.
(1). The fluid-bed reactor provides a uniform temperature profile for The Alphabutol process features are: simple processing, high turn-
optimum catalyst performance. Reaction gases are cooled and filtered to down, ease of operation, low operating pressure and temperature, liquid-
remove small entrained catalyst particles and then routed to the recov- phase operation and carbon steel equipment. The technology has advan-
ery section. Reactor effluent is contacted in an aqueous scrubber (2), tages over other production or supply sources: uniformly high-quality
where essentially 100% of the reactor-made maleic anhydride is recov- product, low impurities, reliable feedstocksource, low capital costs, high
ered as maleic acid. The process has the capabilityof co-producing rnaleic turndown and ease of production.
anhydride (MAH) with the addition of the appropriatepurificationequip-
ment. Scrubber overhead gases are sent to an incinerator for safe disposal. Yields: LLDPE copolymer grade butene-1 is produced with a purity
The resulting maleic acid from the scrubber is then sent directly to exceeding 99.5 wt%. Typical product specification is:
the fured-bed, catalytic hydrogenation reactor (3). Reactor yields exceed Other C4s (butenes + butanes) <0.3 wt%
94% BDO. By adjustments to the hydrogenation reactor and recovery- Ethane <0.15 wt%
purification sections, mixtures of BDO with THF andlor GBL can be Ethylene ~0.05 wt%
directly produced at comparable, overall yields and economics. C6 olefins 4 0 0 ppmw
The hydrogenation reactor effluent is then sent through a series of Ethers (as DME) <2ppmw
distillation steps (4, 5 and 6) to produce final market qualityproduct(s). Sulfur, chlorine dpprnw
Dienes, acetylenes <5ppmw each
Two unique process features are: CO, COz, 0,.HzO,MeOH <5pprnw each
No continuous liquid waste stream to treat-the water separated
in the product purification section is recycled back to the aqueous MAH Economics: Case for a 2002 ISBL investment at a Gulf Coast loca-
scrubber (2). tion for producing 20,000-tpy of butene-l is:
No pretreatment nor post-treatment of the two catalysts is necessary;
Investment, million US) 8
no other chemicals are added.
Raw material
Economics:The GEMINOX BDO technology uses fewer processing Ethylene, tons per ton of butene-I 1.1
steps, as found in competing BDO technologies, leading to significant Byproduds, C6+tons per ton of butene-I 0.08
capital cost savings and lower operating costs. Overall, 2 5 4 0 % cost of qpical operating cost, US) per ton of butene-I 38
production savings are possible compared to competing technologies. The
unique product flexibilityafforded by this process also allows the user to Commercial plants:There are 20 licensed units producing 318,000
quickly meet changing customer and market needs. tpy Sixteen units are in operation; the others are under design or con-
struction.
Commercial plants: BP’s first world-scale 60,000-tpd GEMINOX
BDO plant in Lima, Ohio, has been successfullyoperatingsince July 2000. Licensor: h e n s , h e n s NA.
Licensor: BP Chemicals and Lurgi Oel Gas Chemie GmbH.
282 SEGMENT 3. PETROCHEMICAL PROCESSES

Butyraldehyde, n and i Caprolactam

Application: To produce normal and iso-butyraldehydefrom propy- Application: A process to manufacture caprolactam from nitmtion-
lene and synthesis gas (CO + H2) using the LP 0x0 process, which is a grade toluene. Fiber-grade flaked or molten caprolactam and white
low-pressure, rhodium-catalyzed 0x0 process. ammonium sulfate crystals are produced.
Description: The process reacts propylene with a I:1 syngas at low Description: Toluene and air are fed to the reactor (1) in which the
pressure (<20 kg/cm2g)in the presence of a rhodium catalyst complexed oxidation to benzoic acid is carried out at 160°C and 10 atm. The reac-
with a ligand (1). The oxonation reaction produces normal and iso- tion product is a 30% solution of benzoic acid in toluene plus a small quan-
butyraldehyde in a n/i ratio, which is typically lO:l, but ratios of up to tity of byproducts. Fractionation (2) separates unconverted toluene for
30:1 and down to 1:1 are possible with alternate ligands. The butyralde- recycle, pure benzoic and a bottom fraction of heavy byproducts.
hyde product is removed from the catalyst solution (2) and purified by Benzoic acid is hydrogenated under pressure in presence of palla-
distillation ( 3 ) .N-butyraldehyde is separated from the is0 (4). dium catalyst in a series of continuous stirred tank reactors (3) at 170°C
The process is characterized by its simple flow sheet and Iow-operat- and 16 atm.
ing pressure. This results in low capital and maintenance expenses and Conversion is complete in a single pass. Cyclohexane-carboxylic acid
product cost, and high plant availability. Mild reaction conditions min- is blended with oleum and fed to a multistage reactor (4)where it is con-
imize byproduct formation. Low byproduct formation also contributes to verted to caprolactam by reaction with nitrosylsulhric acid.
higher process efficiencies and product qualities. This acid is produced in a conventional ammonia oxidation plant,
Technology for hydrogenation to normal or iso-butanols or aldoliza- where the nitrogen oxides are absorbed in oleurn.
tion and hydrogenation to 2-ethylhexanol exists and has been widely Reactor effluent is diluted with water (9, and unconverted cyclo-
licensed. A version of the LP 0x0 process has been licensed to produce a hexane carboxylic acid is recycled to the process, while the lactam solution
mixture of C,, alcohols (predominantly 2 propylheptanol) from an n- flows to the crystallization plant (6) where it is neutralized with ammonia.
butene feedstock. Ammonium sulfate crystallizesat bottom and the top organic layer of
caprolactam is recovered and purified through a two-solvent (toluene and
Economics: Typical performance data (per ton of mixed butyralde- water) extraction (7) and a continuous fractionation (8).
hyde):
Economics:Based on a 90,000-tpy battery limits plant, W. Europe,
Feedstocks
Propylene, kg (contained in chemical grade) 600 1990:
Investment, $/tpy 2,800
Synthesis Gas (CO + HJ, Nm3 639 Typical raw material and utility requirements,
per kg of caprolactam:
Commercial plants: The LP 0 x 0 process has been licensed for 19 Toluene, kg 1.08
plants worldwide and is now used to produce more than 60% of the world’s Ammonia, kg 1.14
butyraldehyde capacity. Plants range in size from 30,000 to 350,000 tpy. Sulfur, kg 0.9
The rhodium-basedcatalyst has a long lie, and spent catalysts can be reac- Hydrogen, Nm3 0.8
Ammonium sulfate, kg, (credit) (3.5)
tivated onsite. The technology is also practiced by Union Carbide Corp., Electricity, kWh 0.8
at its Texas City and Taft plants. Steam, kg 11
Fuel gas, Nm3 0.25
Licensees:Nineteen worldwide since 1978. Water, cooling, m3 0.6
Licensor: Davy Process Technology, UWDow Chemical Co., US. Water, chilled, rn3 0.13
Commercial plants: 20,000-tpy SNIA BPD factory in Torviscosa,
Italy; 80,000-tpy ANIC factory in Manfredonia, Italy; expansion to
88,000-tpyELECTROCHIMPROM factory in Chirchik, URSS; 50,000-
tpy plant, Shijiazhuang, China.
Reference: Taverna, M., and M. Chiti, Hydrocarbon Processing,
November 1970, p. 137.
Licensor:SNIA BPD S.p.A., exclusive contractor: SNAICO Engineering
S.P.A.
 SEGMENTS. PETROCHEMICAL PROCESSES 283

Cumene Cumene
Application: Advanced technology to produce high-purity cumene Application: To produce high-quality cumene (isopropylbenzene) by
from propylene and benzene using patented catalytic distillation (CD) alkylating benzene with propylene (typicallyrefinery or chemical grade)
technology.The CDCumene process uses a specially formulated zeolite using liquid-phase Q-Max process based on zeolitic catalyst technology.
alkylation catalyst packaged in a proprietary C D structure and another
specially formulated zeolite transalkylation catalyst in loose form. Description: Benzene is alkylated to cumene over a zeolite catalyst in
a fixed-bed, liquid-phase reactor. Fresh benzene is combined with recy-
Description:The C D column (1) combines reaction and fractiona- cle benzene and fed to the alkylation reactor (1). The benzene feed flows
tion in a single-unit operation. Alkylation takes place isothermally and in series through the beds, while fresh propylene feed is distributed
at low temprature. CD also promotes the continuous removal of reaction equally between the beds. This reaction is highly exothermic, and heat
products from reaction zones. These factors limit byproduct impurities is removed by recycling a portion of reactor effluent to the reactor inlet
and enhance product purity and yield. Low operating temperatures and and injecting cooled reactor effluent between the beds.
pressures also decrease capital investment, improve operational safety and In the fractionation section, propane that accompanies the propylene
minimize fugitive emissions. feedstock is recovered as LPG product from the overhead of the
In the mixed-phase C D reaction system, propylene concentration in depropanizer column (2), unreacted benzene is recovered from the over-
the liquid phase is kept extremely low (cO.1 wt%) due to the higher head of the benzene column (4)and cumene product is taken as over-
volatility of propylene to benzene. This minimizes propylene oligomer- head from the cumene column (5). Di-isopropylbenzene (DIPB) is recov-
ization, the primary cause of catalyst deactivation and results in catalyst run ered in the overhead of the DIPB column (6) and recycled to the
lengths of 3 to 6 years. The vapor-liquid equilibrium effect provides transalkylation reactor (3) where it is transalkylated with benzene over a
propylene dilution unachievable in fixed-bed systems, even with expen- second zeolite catalyst to produce additional cumene. A small quantity of
sive reactor pumparound and/or benzene recycle arrangements. heavy byproduct is recovered from the bottom of the DIPB column (6)and
Overhead vapor from the C D column (1) is condensed and returned is typically blended to fuel oil. The cumene product has a high purity
as reflux after removing propane and lights (P). The CD column bottom (99.96-99.97 wt%), and cumene yields of 99.7 wt% and higher are
section strips benzene from cumene and heavies. The distillation train achieved.
separates cumene product and recovers polyisopropylbenzenes (PIPB) The zeolite catalyst is noncorrosive and operates at mild conditions;
and some heavy aromatics (H) from the net bottoms. PIPB reacts with ben- thus, carbon-steel construction is possible. Catalyst cycle lengths are two
zene in the transalkylator (2) for maximum cumene yield. Operating years and longer. The catalyst is fully regenerablefor an ultimate catalyst
conditions are mild and noncorrosive; standard carbon steel can be used life of six years and longer. Existing plants that use SPA or AlCI, catalyst
for all equipment. I can be revamped to gain the advantages of Q-Max cumene technology
while increasing plant capacity.
Yields: 100,000 metric tons (mt) of cumene are produced from 6$,000
mt of benzene and 35,300 mt of propylene giving a product yield $f over Economics: basis: ISBL US Gulf Coast
99.7%. Cumene product is at least 99.95% pure and has a BromineIndex Investment, USSItpy 40-90
of less than 2, without clay treatment.
Raw materials & utilities, per metric ton of cumene
Economics: Based on a 300,000-mtpy cumene plant located in the Propylene, tons 0.35
US Gulf Coast, the ISBL investment is about US$jYmillion. Benzene, tons 0.66
Electricity, kW 12
vpical operating requirements, per metric ton of cumene: Steam, tons (import) 0.7
Propylene 0.353
Water, cooling, m3 3
Benzene 0.650
Yield 99.7% The Q-Max design is typically tailored to provide optimal utility
Utilities: advantage for the plant site, such as minimizing heat input for stand-
Electricity, kWh 8 alone operation or recovering heat as steam for usage in a nearby phenol
Heat (Import), lo6 kcal 0.5 plant.
Steam (export), mt 1 .o
Water, cooling, m3 12 Commercial plants: Seven Q-Max units are in operation with a total
cumene capacity of 2.3 million tpy, and two additional units are either
Commercial plants: Formosa Chemicals & Fibre Corporation, in design or under construction.
TaiWan-270,OOO mtpy
Licensor: UOP LLC.
Licensor:CDTECH, a partnership between ABB Lummus Global and
Chemical Research & Licensing.
284 SEGMENT 3. PETROCHEMICAL PROCESSES

Cumene Cyclohexane
Application: To produce cumene from benzene and any grade of Application: Produce high-purity cyclohexane by liquid-phase cat-
propylene-including lower-quality refinery propylene-propane mix- alytic hydrogenation of benzene.
tures-using the MobillBadger process and a new generation of zeolite
catalysts from ExxonMobil. Description: The main reactor (1) converts essentially all the feed
isothermally in the liquid phase at a thermodynamically-favorablelow tem-
Description: The process includes: a fxed-bed alkylation reactor, a perature using a continuously-injected soluble catalyst. The catalyst’s
fixed-bed transakylation reactor and a distillation section. Liquid propy- high activity allows use of low hydrogen partial pressure, which results
lene and benzene are premixed and fed to the alkylation reactor (1) in fewer side reactions, e.g., isomerization or hydrocracking. The heat of
where propylene is completely reacted. Separately, recycled polyiso- reaction v a p r i i cydohexane product and, using pumparound circulation
propylbenzene(PIPB) is premixed with benzene and fed to the transaky- through an exchanger, also generates steam (2). With the heat of reaction
lation reactor (2) where PIPB reacts to form additional cumene. The being immediately removed by vaporization, accurate temperature con-
transalkylation and alkylation effluents are fed to the distillation section. trol is assured. A vapor-phase fixed-bed finishing reactor (3) completes
The distillation section consists of as many as four columns in series. The the catalytic hydrogenation of any residual benzene. This step reduces resid-
depropanizer (3) recovers propane overhead as LPG. The benzene col- ual benzene in the cyclohexane product to very low levels. Depending on
umn (4)recovers excess benzene for recycle to the reactors. The cumene the purity of the hydrogen make-up gas, the stabilizationsection includes
column (5) recovers cumene product overhead. The PIPB column (6) either an LP separator (4)or a small stabilizer to remove the light ends.
recovers PIPB overhead for recycle to the transalkylation reactor. A prime advantage of the liquid-phaseprocess is its substantially lower
cost compared to vapor phase processes: investment is particularly low
Process features: The process allows a substantial increase in capac- because a single, inexpensivemain reactor chamber is used compared to
ity for existing SPA, AICI,, or other zeolite cumene plants while improv- multiple-bed or tubular reactors used in vapor phase processes. Quench
ing product purity, feedstock consumption, and utility consumption.The gas and unreacted benzene recycles are not necessary and better heat
new catalyst is environmentally inert, does not produce byproduct recovery generates both the cydohexane vapor for the finishing step and
oligomers or coke and can operate at extremely low benzene to propy- a greater amount of steam. These advantages result in lower investment and
lene ratios with proven commercial cycle lengths of over five years. operating costs. Operational flexibility and reliability are excellent; changes
Expected catalyst life is well over five years. in feedstock quality and flows are easily handled. Should the catalyst be
Yield and product purity: Thisprocess is essentiallystoichiometric deactivated by feed quality upsets, fresh catalyst can be injected without
and product purity above 99.97% weight has been regularly achieved in shutting down.
commercial operation. Yield: 1.075 kg of cyclohexane is produced from 1 kg of benzene.
Economics:Estimated ISBL investment for a 300,000-mtpy unit on Economics: Basis: 200,000-tpy cyclohexane complex, ISBL 2002
the US Gulf Coast (2002 construction basis), is US$15 million. Gulf Coast location with PSA hydrogen is US$7.8 million. Catalyst cost
Utility requirements, per ton of cumene product: is US$ 1.2lmetric ton of product.
Heat, MMkcal (import) 0.32 Commercial plants: Thirty-one cyclohexane units have been
Steam, ton (export) (0.60) licensed.
The utilities can be optimized for specific site conditionsleconomicsand Licensor: Axens, Axens NA.
integrated with an associated phenol plant.
Commercial plants: The first commercial application of this pro-
cess came onstream in 1996.At present, there are 11 phnts operating with
a combined capacityexceeding 4.7 million mtpy. In addition, two grass-
roots plants and an SPA plant revamp are in the design phase. Fifty per-
cent of the worldwide cumene production is from plants using the
MobillBadger process.
Licensor:The Badger Technology Center of Washington Group Inter-
national, Inc.
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SEGMENTS. PETROCHEMICAL PROCESSES 285

Dimethyl terephthalate Dimethylformamide

Application: To increase capacity and reduce energy usage of exist- Application: To produce dimethylformamide (DMF) from dimethy-
ing or grassroots dimethyl terephthalate(DMT) production facilities using lamine (DMA) and carbon monoxide (CO).
variations of GT-DMT proprietary technology.
Description:Anhydrous DMA and CO are continuously fed to a spe-
Description: The common production method of DMT from paraxy- cialized reactor (I), operating at moderate conditions and containing a
lene and methanol is through successive oxidations in four major steps: catalyst dissolved in solvent. The reactor products are sent to a separa-
oxidation, esterification, distillation and crystallization.A mixture of p- tion system where crude product is vaporized (2) to separate the spent
xylene and methyl p-toluate (MPT) is oxidized with air using a heavy- catalyst. Excess DMA and catalyst solvent are stripped (3) from the
metal catalyst. All organics are recovered from the offgas and recycled to crude product and recycled back to the reaction system. Vacuum distil-
the system. The acid mixture from the oxidation is esterified with lation (4)followed by further purification (5) produces a high-qualitysol-
methanol and produces a mixture of esters. The crude ester mixture is dis- vent and fiber-grade DMF product. A saleable byproduct stream is also
tilled to remove all heavy boilers and residue produced: lighter esters are produced.
recycled to the oxidation section. Raw DMT is then sent to the crystal-
lization section to remove DMT isomers and aromatic aldehydes. Yields: Greater than 95% on raw materials. CO yield is a function of
The technology improvements enhance the traditional processing in its quality.
each section. The adaptations include: changes in process configurations Economics: Typical performance data per ton of product:
and operating conditions, alterating the separation schemes, revising the
recovery arrangement, increasing the value of the byproducts and reduc- Dimethylamine, t 0.63
ing the overall plant recycles. Carbon monoxide, t 0.41
GTC Technologyoffers complete implementation of the technology Steam, t 1.3
Water, cooling, m3 100
and overall plant reviews for selective improvements to reduce operating Electricity, kWh 10
and overall production costs. Some separate improvements available are:
1. Oxidation optimization reduces byproduct formation, thus low- Commercial plants: Thirteen plants in eight countries use this pro-
ering p-xylene consumption cess with a production capacity exceeding 100,000 mtpy.
2. Recoveries of byproducts for sale such as methyl benzoate (MeBz)
and acetic and formic acid Licensor: Davy Process Technology, UK.
3. Improved esterifier reactor design enables higher throughputs and
improves methanol usage
4. Enhanced isomer removal minimizes DMT losses
5. Improved crystallization schemes for reduced energy, lowers
methanol handling and losses, improves purity and operating flexibility
6. Integration of steam usage in the plant for considerable savings on
operating costs
7. Operating reviews to reduce operating downtime and extend online
factors
8. Advanced control models for improved operability.
Economics: Based on process modifications, an existing DMT plant
can increase production with an investment of $200 to $600/t0n/yr of
additional capacity. A new plant will have an investment reduction of about
20% equipment cost. Raw material consumptionper ton of product (with
the complete modification) is 605 ton of paraxylene and 360 ton of
methanol.
Commercial plants: GT-DMT technology is used by seven DMT
producers.
Licensor: GTC Technology Inc.