Parte 4

Petrochemical Processes 2010 Home Process Categories Company Index

Normal paraffins, C10 – C13

Application: The Molex process recovers normal C10 – C13 paraffins
from kerosine using UOP’s innovative Sorbex adsorptive separation
technology. Makeup hydrogen Light ends
Recycle gas
Light kerosine
Description: Straight-run kerosine is fed to a stripper (1) and a rerun col-
umn (2) to remove light and heavy materials. The remaining heart-cut Normal paraffin
kerosine is heated in a charge heater (3) and then treated in a Union- Straight-run
kerosine
fining reactor (4) to remove impurities. The reactor effluent is sent to a 1 2 3 4 5 6 7
product separator (5) to separate gas for recycle, and then the liquid is Raffinate
sent to a product stripper (6) to remove light ends. The bottoms stream
from the product stripper is sent to a Molex unit (7) to recover normal Heavy
paraffins. kerosine
Feedstock is typically straight-run kerosine with 18 – 50% normal

paraffin content. Product purity is typically greater than 99 wt%.
Economics: Investment, US Gulf Coast inside battery limits for the pro-
duction of 100,000 tpy of normal paraffins: 1,000 $/tpy
Commercial plants: Thirty-two Molex units have been built.

Licensor: UOP LLC, A Honeywell Company - CONTACT
Copyright © 2010 Gulf Publishing Company. All rights reserved.

n-Paraffin Ammonia
LAB grade n-paraffins product
Desorbent
Application: Efficient low-cost recovery and purification processes for Molecular
the production of linear alkylbenzene (LAB)-grade and/or high-purity sieve beds Adsorption
Desorption
normal-paraffin (n-paraffin) products from kerosine.
Jet fuel
Desorption
Description: The ExxonMobil Chemical (EMC) process offers commer- to refinery
cially proven technologies for efficient recovery and purification of Jet fuel
Adsorption to refinery
high-purity n-paraffin from kerosine feedstock. Kerosine feedstocks are Molecular
introduced to the proprietary ENSORB recovery process developed by sieve beds
Kerosine feed High-purity
ExxonMobil Chemical, wherein the long-chain aliphatic normal paraf- n-paraffins
fins are selectively removed from the kerosine stream in vapor phase by Recovery Purification product
section section
adsorption onto a molecular sieve. Isoparaffins, cycloparaffins, aromat-
ics and other components not adsorbed are typically returned to the
refinery kerosine pool. The cyclical process uses a low pressure ammonia weights, and an optimized post-recovery fractionation section allows
desorbate to recover the n-paraffins from the sieve for use as LAB-qual- for fine-tuning of product compositions. The need for a sharp cut in a
ity product or for further purification. front-end fractionation section is eliminated, thereby reducing the en-
Significant savings in capital cost are achieved by minimizing the ergy consumption of the process.
need for feed pretreatment before the kerosine enters the recovery sys-
tem. The ENSORB process exhibits a high tolerance to feed impurities, Product quality: The technology produces n-paraffins suitable for LAB pro-
up to 400 ppmwt sulfur and 80 ppmwt nitrogen. For feedstocks with duction and other specialty applications. The typical product quality is:
higher sulfur and nitrogen content, only mild hydrotreating is needed to Purity, wt% 99
reduce the impurity levels in the kerosine feed to an acceptable range. Aromatics, ppmwt < 100
The robust adsorbent is able to last long cycle lengths with a total life up Bromine Index, mg/100g < 20
to 20 years, as commercially demonstrated by ExxonMobil. Sulfur, ppmwt <1
The LAB-grade product from the recovery process is further pro-
cessed in an optional purification section, where residual aromatics and Yield: The highly selective proprietary molecular sieves offer recovery of
other impurities are further reduced to below 100 ppmwt. Purification 99 wt% n-paraffin for LAB quality product.
is accomplished in a liquid-phase, fixed-bed adsorption system. The im- Commercial plants: EMCC was the first commercial producer of n-par-
purities are selectively adsorbed on a molecular sieve, and subsequently affins and one of the world’s largest producers for over 40 years, oper-
removed with a hydrocarbon desorbent. ating a single train plant in Baytown, Texas, with a capacity of 400,000
The ENSORB adsorbent offers a high recovery of n-paraffins and metric tpy.
a tolerance for sulfur and nitrogen that is unparalleled in the industry.
Process conditions can be optimized for a targeted range of molecular Licensor: Kellogg Brown & Root LLC - CONTACT
Octenes
Application: The Dimersol-X process transforms butenes into octenes,
which are ultimately used in the manufacture of plasticizers via Reaction Catalyst Separation
section removal section C4
isononanol (isononyl alcohol) and diisononyl phthalate units.
Description: Butenes from fluid catalytic cracking (FCC) or steam crack- Octenes
ing are dimerized into a liquid-phase oligomerization unit comprising
three sections. In the reaction section, dimerization takes place in mul- 2 2 3
tiple liquid-phase reactors (1) using homogeneous catalysis and an ef-
1
ficient recycle mixing system. The catalyst is generated in situ by the 4
reaction of components injected in the recycle loop. The catalyst in the Catalyst
reactor effluent is deactivated in the neutralization section and sepa- Butenes
Caustic Purge
rated for safe disposal (2). Process water
C12
The stabilization section (3) separates unreacted olefin monomer and water
saturates from product dimers, while the second column (4) separates
the octenes. A third column can be added to separate dodecenes.
Yields: Nearly 80% conversion of n-butenes can be attained and se-

lectivities toward octenes are about 85%. The typical C8 product is a
mixture having a minimum of 98.5% octene isomers with the following
distribution: Commercial plants: Thirty-six Dimersol units treating various olefinic C3
n-Octenes 7% and C4 cuts have been licensed. Typical octenes production capacities
Methyl-heptenes 58% range from 20,000 tpy up to 90,000 tpy.
Dimethyl-hexenes 35%
Reference: Convers, A., D. Commereuc and B. Torck, “Homogeneous
Dimersol-X octenes exhibit a low degree of branching, resulting in
Catalysis,” IFP Conference.
higher downstream oxonation reaction yields and rates, and better plas-
ticizer quality. Licensor: Axens - CONTACT
Economics: Basis: ISBL 2010 for a Gulf Coast location using 50,000 tpy
of a raffinate-2 C4 cut containing 75% n-butenes.
Investment, US$ million 8
Typical operating cost, US$ 60 per metric ton of octenes

Olefins—butenes extractive distillation

Application: Separation of pure C4 olefins from olefinic/paraffinic C4 C4 paraffins
mixtures via extractive distillation using a selective solvent. BUTENEX
is the Uhde technology to separate light olefins from various C4 feed-
stocks, which include ethylene cracker and FCC sources.
Description: In the extractive distillation (ED) process, a single-com- C4 olefins

pound solvent, N-Formylmorpholine (NFM), or NFM in a mixture with C4 Extractive
fraction distillation Stripper
further morpholine derivatives, alters the vapor pressure of the com- column column
ponents being separated. The vapor pressure of the olefins is lowered
more than that of the less soluble paraffins. Paraffinic vapors leave the
top of the ED column, and solvent with olefins leaves the bottom of the
ED column.
The bottom product of the ED column is fed to the stripper to Solvent + olefins
Solvent
separate pure olefins (mixtures) from the solvent. After intensive heat
exchange, the lean solvent is recycled to the ED column. The solvent,
which can be either NFM or a mixture including NFM, perfectly satisfies
the solvent properties needed for this process, including high selectivity,
thermal stability and a suitable boiling point.
Economics:
Consumption per metric ton of FCC C4 fraction feedstock:
Steam, t / t 0.5 – 0.8
Water, cooling ( DT = 10°C ), m3/ t 15.0
Electric power, kWh/t 25.0
Product purity:
n - Butene content 99.+ wt.– % min.
Solvent content 1 wt.– ppm max.
Commercial plants: Two commercial plants for the recovery of n - butenes

have been installed since 1998.
Licensor: Uhde GmbH - CONTACT

Olefins by dehydrogenation
HP steam
Application: The Uhde STeam Active Reforming STAR process produces Air
(a) propylene as feedstock for polypropylene, propylene oxide, cumene, Fuel gas
acrylonitrile or other propylene derivatives, and (b) butylenes as feed- Feed Raw gas
preheater compression
stock for methyl tertiary butyl ether (MTBE), alkylate, isooctane, polybu- Star Fuel gas
reformer
tylenes or other butylene derivatives.
O2/air
Feed: Liquefied petroleum gas (LPG) from gas fields, gas condensate
Oxy Heat Gas
fields and refineries. reactor recovery separation
Product: Propylene (polymer- or chemical-grade); isobutylene; n-buty- Hydrocarbon feed

Olefin
lenes; high-purity hydrogen (H2) may also be produced as a byproduct. Boiler feed water product
Fractionation
Process condensate
Description: The fresh paraffin feedstock is combined with paraffin re- Process steam Hydrocarbon
cycle and internally generated steam. After preheating, the feed is sent recycle
to the reaction section. This section consists of an externally fired tubu-
lar fixed-bed reactor (Uhde reformer) connected in series with an adia-
batic fixed-bed oxyreactor (secondary reformer type). In the reformer,
the endothermic dehydrogenation reaction takes place over a propri- After cooling and condensate separation, the product is subse-
etary, noble metal catalyst. quently compressed, light-ends are separated and the olefin product is
In the adiabatic oxyreactor, part of the hydrogen from the interme- separated from unconverted paraffins in the fractionation section.
diate product leaving the reformer is selectively converted with added Apart from light-ends, which are internally used as fuel gas, the
oxygen or air, thereby forming steam. This is followed by further de- olefin is the only product. High-purity H2 may optionally be recoverd
hydrogenation over the same noble-metal catalyst. Exothermic selec- from light-ends in the gas separation section.
tive H2 conversion in the oxyreactor increases olefin product space-time
yield and supplies heat for further endothermic dehydrogenation. The Economics: Typical specific consumption figures (for polymer-grade
reaction takes place at temperatures between 500°C– 600°C and at 4 propylene production) are shown (per metric ton of propylene product,
bar – 6 bar. including production of oxygen and all steam required):
The Uhde reformer is top-fired and has a proprietary “cold” out- Propane, kg/metric ton 1,200
let manifold system to enhance reliability. Heat recovery utilizes process Fuel gas,GJ/metric ton 6.4
heat for high-pressure steam generation, feed preheat and for heat re- Circul. cooling water, m3/metric ton 220
quired in the fractionation section. Electrical energy, kWh/metric ton 180
Continued 

Olefins by dehydrogenation, continued
Commercial plants: Two commercial plants using the STAR process for
dehydrogenation of isobutane to isobutylene have been commissioned
(in the US and Argentina). More than 60 Uhde reformers and 25 Uhde
secondary reformers have been constructed worldwide.
References: Heinritz-Adrian, M., N. Thiagarajan, S. Wenzel and H. Gehrke,

“STAR—Uhde’s dehydrogenation technology (an alternative route to C3-
and C4-olefins),” ERTC Petrochemical 2003, Paris, France, March 2003.
Thiagarajan, N., U. Ranke and F. Ennenbach, “Propane/butane de-
hydrogenation by steam active reforming,” Achema 2000, Frankfurt,
Germany, May 2000.
Licensor: Uhde GmbH - CONTACT

Olefins—Catalytic
Application: To selectively convert vacuum gasoils, paraffinic residual
feedstocks and resulting blends of each into C2–C5 olefins, aromatic-
rich, high-octane gasoline and distillate using the Deep Catalytic Crack-
ing (DCC) process.
Description: The DCC process selectively cracks a wide variety of feed-

stocks into light olefins, with a reactor/regenerator configuration similar
to traditional fluid catalytic cracking (FCC) units (see figure). Innovations
in catalyst development and process variable selection lead to synergistic
benefits and enable the DCC process to produce significantly more ole-
fins than an FCC that is operated for maximum olefins production.
The DCC process was originally developed by the Research Institute
of Petroleum Processing (RIPP) and Sinopec in the People’s Republic of
China. Shaw’s Energy and Chemicals Group is the sole engineering con-
tractor licensed to offer DCC technology outside of China.
DCC units may be operated in two modes: maximum propylene (Type
I) or maximum iso-olefins (Type II). Each operational mode utilizes unique
catalyst as well as specific reaction conditions. DCC-I uses both riser and
bed cracking at more severe reactor conditions, while DCC-II utilizes only
riser cracking like a modern FCC unit at milder conditions. The DCC pro-
cess applies specially designed and patented zeolite catalysts.
The reaction temperature in DCC is higher than that of conven-
tional FCC but much lower than that of steam cracking. Propylene yields
over 20 wt% are achievable with paraffinic feeds. Ethylene yield is much
higher than the conventional FCC process. The DCC-mixed C4s stream Table 1. Olefin yields for DCC modes
also contains increased amounts of butylenes and iso-C4s as compared Products, DCC Type I DCC Type II FCC
to an FCC. The high olefin yields are achieved by deeper cracking into wt% fresh feed
the aliphatic components of the naphtha and LCO. The dry gas pro- Ethylene 6.1 2.3 0.9
duced from the DCC process contains approximately 50% ethylene. Propylene 20.5 14.3 6.8
The cracking reactions are endothermic, and compared to FCC, a higher Butylene 14.3 14.6 11
coke make is required to satisfy the heat balance. Table 1 summarizes in which Isobutylene 5.4 6.1 3.3
typical olefins yields for DCC with FCC. Continued 
Olefins—Catalytic, continued
This technology is suitable for revamps as well as grassroots applica-
tions. The DCC process is very suitable for integration with an ethylene
plant—refer to “HOFCC and Ethylene Plant Integration” for the ben-
efits of capital reduction and production efficiency.
Commercial plants: At present, eight units are in operation: six in China,

one in Thailand and one in Saudi Arabia. Another six plants are in de-
sign or construction. The unit in Saudi Arabia is the largest DCC unit in
the world.
Reference: Dharra, et al., “Increase Light Olefins Production,” Hydro-

carbon Processing, April 2004.
Licensor: The Shaw Group - CONTACT

Paraxylene
Application: Suite of advanced aromatics technologies combined in the Raffinate
4
most effective manner to meet customers’ investment and production Benzene
BT
objectives for paraxylene (PX) and benzene and are licensed under the extraction
name ParamaX. Paraxylene
C7–
Description: Aromatics are produced from naphtha in the Aromizing Toluene
section (1), and separated by conventional distillation. The xylene frac- H2 C8+
PX Tol-C11
extraction transalkylation
tion is sent to the Eluxyl unit (2), which produces 99.9% PX via simulat- 2
ed countercurrent adsorption. The PX-depleted raffinate is isomerized Naphtha
C8 5
Reforming
back to equilibrium in the isomerization section (3) with either ethylben- C9+C10
zene (EB) dealkylation-type (XyMax) processes or EB isomerization-type 1 C8 C8
C8+ isom.
(Oparis) catalysts. High-purity benzene and toluene are separated from
non-aromatic compounds with extractive distillation (Morphylane**) 3
Heavy aromatics
C9+ C10+
processes (4). Toluene and C9 to C11 aromatics are converted to higher
valued benzene and mixed xylenes in the TransPlus* process (5), leading
to incremental PX production.
Eluxyl technology has the industrially proven ability to meet ultimate
single-train PX purity and capacities as high as 840,000 metric tpy. Pro-
prietary hybrid Eluxyl configurations integrate an intermediate purity ad-
Reference: Leflour,T., N. Yomoji and J. Rault “Fast-track ParamaX imple-
sorption section with single-stage crystallization, ideal for retrofits. Ax-
mentation at Kashima Oil Refinery,” ERTC Petrochemical Conference,
ens is the licensor of all the technologies involved in the ParamaX suite.
Rome 2009.
Production: Typical paraxylene single-train complex from naphtha to PX,
Licensor: Axens - CONTACT
featuring Aromizing, Eluxyl, XyMax and TransPlus units.
*
Mobil and **Uhde technologies licensed by Axens for grassroots applications
Commercial plants: Eleven ParamaX integrated plants have been li-
censed, accounting for more than 10 million tpy of PX. Three ParamaX
integrated plants are in operation. Ten Eluxyl units are in commercial
operation with single-line capacity ranging from 180,000 metric tpy to
840,000 metric tpy of PX. Oparis has been selected in 17 plants in both
retrofits and grassroots applications. There are 18 XyMax and 16 Trans-
Plus references.

Paraxylene
Application: To selectively convert toluene to high-purity (90%+) para-
xylene-rich xylenes and benzene using ExxonMobil Chemical’s technol- Hydrogen makeup
Hydrogen recycle To fuel system
ogies—PxMax and ASTDP.
CW
Description: Dry toluene feed and hydrogen-rich recycle gas are pumped
through feed/effluent exchangers and charge heater and into the reac-
tor (1). Selective toluene disproportionation (STDP) occurs in the vapor CW
phase to produce the paraxylene-rich xylene and benzene co-product. 3
Stabilizer
Byproduct yields are small. Toluene feed 1 2
Reactor effluent is cooled by heat exchange, and liquid products
are separated from the recycle gas. Hydrogen-rich gas from the sepa- Furnace
rator (2) is recycled back to the reactor together with makeup hydro- Product
fractionation
gen. Liquid product is stripped of remaining light gas in the stabilizer Reactor Separator
(3) and sent to product fractionation. Unconverted toluene is recycled
to extinction.
The PxMax technology uses catalyst, which is ex-situ selectivated
by pretreatment during catalyst manufacture. The ASTDP technology
uses catalyst, which is in-situ coke selectivated. Both technologies pro-
vide significantly higher selectivity and longer operating cycles than two PxMax units started up in 1996 and 1997 at Chalmette Refining’s
other STDP technologies. Operating costs associated with downstream Louisiana refinery and Mobil Chemical’s Beaumont plant, respectively.
recovery are also reduced by the high-purity paraxylene from PxMax
and ASTDP. Licensor: ExxonMobil Chemical Technology Licensing LLC (retrofit ap-
plications)
Operating conditions: PxMax operates at lower start-of-cycle tempera- Axens (grassroots applications) - CONTACT
tures and lower hydrogen to hydrocarbon recycle ratios than other STDP
technologies, resulting in longer cycles and lower utilities. By eliminat-
ing the in-situ selectivation step, the PxMax version of this technology
results in simplified operation and lower capital costs. Both catalysts
offer long operating cycles and are regenerable.
Commercial plants: There are four MSTDP units (predecessor technology

to PxMax), and ASTDP and eight units using PxMax technology. The first

Paraxylene
Application: To selectively convert toluene to high-purity (90%+) par- Hydrogen makeup
Hydrogen recycle To fuel system
axylene-rich (PX) xylenes and benzene using ExxonMobil Chemical’s Px-
Max technology. CW
Description: Dry toluene feed and hydrogen-rich recycle gas are pumped
through feed/effluent exchangers and charge heater and into the reac-
tor (1). Selective toluene disproportionation (STDP) occurs in the vapor CW
phase to produce the paraxylene-rich xylene and benzene co-product. 3
Stabilizer
Toluene 2
Byproduct yields are small. Reactor effluent is cooled by heat exchange feed 1
and liquid products are separated from the recycle gas. Hydrogen-rich
Furnace
gas from the separator (2) is recycled back to the reactor together with
makeup hydrogen. Liquid product is stripped of remaining light gas in
Product
the stabilizer (3) and sent to product fractionation. Unconverted toluene fractionation
Reactor Separator
is recycled to extinction.
The PxMax technology uses catalyst, which is permenately selectivated
by ex-situ pretreatment during catalyst manufacture. PxMax technology
provides significantly higher selectivity and longer operating cycles than
other STDP technologies. Operating costs associated with downstream
recovery are also reduced by the high paraxylene purity from PxMax.
Licensor: ExxonMobil Chemical Technology Licensing LLC (retrofit ap-
Operating conditions: PxMax operates at lower start-of-cycle tempera- plications) - CONTACT
tures and lower hydrogen to hydrocarbon recycle ratios than other STDP Axens (grassroots applications)
technologies, resulting in longer cycles and lower utilities. By eliminating
the in-situ selectivation step, the PxMax technology results in simplified
operation and lower capital costs. The catalyst offers long operating
cycles and is regenerable.
Commercial plants: There are three MSTDP units (predecessor technol-

ogy to PxMax) and ten PxMax units are currently in operation. The first
two PxMax units started up in 1996 and 1997 at Chalmette Refining’s
Louisiana Refinery and Mobil Chemical’s Beaumont plant, respectively.

Paraxylene Sulfolane
Raffinate
Benzene
4
Application: A UOP aromatics complex is a combination of process units Toluene
Hydrogen
which are used to convert petroleum naphtha and pyrolysis gasoline
into the basic petrochemical intermediates: benzene, toluene, paraxy- CCR Tatoray
8
platforming
lene and/or ortho-xylene. 2 3 5 6 7
THDA
Description: The configuration of an aromatics complex depends upon Naphtha 9
hydrotreating Aromatics C10+
the available feedstock, the desired product slate, and the balance be- 1
Paraxylene
tween performance and capital investment. A fully integrated modern
Naphtha Light ends
complex contains a number of UOP process technologies. Parex Isomar
11 12
The naphtha feed is first sent to a UOP naphtha hydrotreating
O-xylene
unit (1) to remove sulfur and nitrogen compounds and then sent to a
13
UOP CCR Platforming unit (2) to reform paraffins and naphthenes to 10
aromatics.
14
The reformate produced in the CCR Platforming unit is sent
to a stabilizer column, which strips off the light ends. The stabilizer
bottoms are sent to a reformate splitter (3). The C7 fraction from the
overhead of the reformate splitter is sent to a Sulfolane unit (4). The
C8+ fraction from the bottom of the reformate splitter is sent to a xylene
fractionation section. The UOP Sulfolane unit extracts the aromatics and The xylene splitter overhead is sent directly to a Parex unit (11),
then individual high-purity benzene and toluene products are recovered where 99.9 wt% pure paraxylene is recovered by adsorptive separation
in a BT fractionation section (5 & 6). at very high recovery. The raffinate from the Parex unit is almost
Toluene is usually blended with C9+ aromatics (A 9+) from the entirely depleted of paraxylene and is sent to an Isomar unit (12). In
overhead of the heavy aromatics column (7) and charged to a Tatoray the Isomar unit, additional paraxylene is produced by re-establishing
unit (8) for production of additional xylenes and benzene. Toluene and an equilibrium distribution of xylene isomers. The effluent from the
heavy aromatics can also be charged to a THDA unit (9) for production Isomar unit is sent to a deheptanizer column (13). The bottoms from
of additional benzene. the deheptanizer are recycled back to the xylene splitter column.
The C 8+ fraction from the bottom of the reformate splitter is
charged to a xylene splitter column (10). The bottom of the xylene Economics: A summary of the investment cost and the utility consump-
splitter column is sent to the o-xylene column (14) to separate high- tion for a typical paraxylene aromatics complex to process 1.5 million
purity o-xylene product and the bottoms are sent to the heavy aromatics meric tpy of naphtha feed is indicated below. The estimated ISBL erected
column (7). cost for the unit assumes construction on a US Gulf coast site in 2009.
Continued 
Paraxylene, continued
Investment, US$ million 363

Products, metric tpy
Raffinate 252,000
LPG 68,000
Benzene 264,000
Paraxylene 700,000
Pure hydrogen 49,000
Utilities, per metric ton of feed
Electricity, kWh 64.3
Steam, metric ton (–0.37)
Water, cooling, m3 5.7
Fuel, Gcal 1.6
Commercial plants: UOP is the world’s leading licensor of process tech-

nology for aromatics production. UOP has licensed more than 600 sepa-
rate process units for aromatics production, including over 260 CCR
Platforming units, 139 Sulfolane units, 93 Parex units, 75 Isomar units,
54 Tatoray units and 38 THDA units.
UOP has designed 93 integrated aromatics complexes, which
produce both benzene and paraxylene. These complexes range in
paraxylene production capacity from 21,000 to 1.7 million metric tpy.
Licensor: UOP LLC, A Honeywell Company - CONTACT

Paraxylene H2 makeup C 7–
Application: To produce a desired xylene isomer (or isomers) from a mix-
ture of C8 aromatics using the UOP Isomar and Parex processes.
Description: Fresh feed containing an equilibrium mixture of C8 aro- 3 4 5 6

matic isomers is fed to a xylene splitter (1). Bottoms from the splitter
C8 aromatics p-Xylene
are then separated (2) into an overhead product of o-xylene and a by- 1
product of C9+ aromatics. Overhead from the splitter is sent to a UOP o-Xylene
Parex process unit (3) to recover ultra-high-purity p-xylene. If desired,
high-purity m-xylene may also be recovered using the MX Sorbex pro- 2
cess. Remaining components are recycled to the UOP Isomar process
unit reactor (4) where they are catalytically converted back toward an C9+ aromatics
equilibrium mixture of C8 aromatic isomers. Hydrogen-rich recycle gas

is separated (5) from the reactor effluent before fractionation (6) to re-
move light-cracked byproducts overhead. The remaining C8 aromatics
are then combined with the fresh feed and sent to the xylene splitter Yields: Typical yields of key products from a Parex-Isomar complex:
(1).
Composition Fresh feed, wt. units Product, wt. units
The feedstock consists of a mixture of C8 aromatics typically derived
Benzene – –
from catalytically reformed naphtha, hydrotreated pyrolysis gasoline or an
Ethylbenzene 17.2 –
LPG aromatization unit. The feed may contain up to 40% ethylbenzene,
p-Xylene 18.3 78.8
which is converted either to xylenes or benzene by the Isomar reactor at
m-Xylene 41.8 –
a high-conversion rate per pass. Feedstocks may be pure solvent extracts
o-Xylene 22.7 10
or fractional heartcuts containing up to 25% nonaromatics. Hydrogen
may be supplied from a catalytic reforming unit or any suitable source. Economics: Estimated inside battery limits (ISBL) erected and utility costs
Chemical hydrogen consumption is minimal. are given for a Parex-Isomar complex which includes the xylene column,
o-Xylene product purity of up to 99% is possible, depending on US Gulf Coast site in 2009.
the composition of the feed and fractionation efficiency. The Parex unit Investment, US$ per metric ton of feed 150–200
is capable of producing 99.9% pure p-xylene with per pass recovery Utilities, US$ per metric ton of p-xylene product 30
greater than 97%.
Commercial plants: Since 1971, UOP has licensed 93 Parex units and 75
Operating conditions: Moderate temperature and pressure require- Isomar units.
ments permit using carbon and low-alloy steel and conventional process
equipment. Licensor: UOP LLC, A Honeywell Company - CONTACT
Paraxylene Light ends
Benzene
Application: The UOP PX-Plus XP Process converts toluene to par- Hydrogen
Paraxylene
axylene and benzene. The paraxylene is purified to 99.9+ wt% via
single-stage crystallization and a wash column. The benzene purity Toluene
is 545-grade by fractionation. 1 2 3
Description: The PX-Plus XP Process is composed of three processing

Recycle toluene Heavies Mother liquor
steps:
(1) Selective toluene disproportionation, via the PX-Plus Process
(2) Fractionation for recovery of recycle toluene and benzene
product Yields:
(3) The Badger/Niro paraxylene crystallization process, where Toluene conversion per pass 30%
single-stage crystallization and crystal wash columns are used. Paraxylene yield, wt% 36
In the PX-Plus technology, fresh toluene is combined with Benzene yield, wt% 43
recycle gas, heated and fed to a fixed-bed reactor. The para- Light ends, wt% <8
selective catalyst produces xylene product with 90% paraxylene in Paraxylene recovery 93.5%
the xylenes. Reactor effluent flows to a separator, where the recycle Paraxylene purity, wt% 99.9
gas is recovered, and the liquid product is sent to a stripper.
In the fractionation section, stripper bottoms are fed to a
Economics: Capital investment per metic tpy of paraxylene product
EEC, US$ 285
benzene column, where the benzene product is recovered and
Utilities per mt of paraxylene product
the unconverted toluene is fractionated for recycle. The toluene
Electricity, kWh 172
column bottoms are sent to a rerun column where the paraxylene
Steam, HP, metric ton 2.48
concentrated fraction is taken overhead.
Steam, LP, metric ton 3.76
In the Badger/Niro crystallization unit, the xylenes are fed
Water, cooling, m3 27
to a single-stage crystallization section that uses continuous
Fuel, MMkcal 0.5
suspension crystallization. In this section, the paraxylene is purified
with a single refrigerant compressor system, and the mother Commercial plants: Three PX-Plus units have been brought online. Two
liquor rejected. The purified paraxylene is fed to a Niro wash Badger/Niro licensed and process packages were produced for three
column section where ultra-high-purity paraxylene is produced by Badger/Niro crystallization projects.
countercurrent crystal washing.
Components of this flexible technology are especially suited for Licensor: UOP LLC, A Honeywell Company, The Shaw Group, Inc., and
capacity expansion of existing paraxylene production facilities. Niro Process Technology B.V. - CONTACT

Paraxylene, crystallization Primary

Application: CrystPX is a modern suspension crystallization technology centrifuge
for production of paraxylene (PX). The process can be applied in a sin-

gle-stage for concentrated PX feedstock or in two stages for equilibrium
(Slurry)
(Cake)
xylenes feed. The technology has fewer pieces of equipment, simplified
(Slurry)
flow schemes, and a more reliable operation compared to traditional
crystallization methods. PX-lean filtrate
PX melt
Description: Suspension crystallization of PX in the xylene isomer mix-
ture is used to produce PX crystals. The technology utilizes an optimized PX-rich feed (Cake)
arrangement of equipment to obtain the required recovery and product

purity. Washing the paraxylene crystal with the final product in a high- Feed
drum
efficiency pusher-centrifuge system produces the paraxylene product.
When PX content in the feed is enriched above equilibrium, such PX product
as streams originating from selective toluene conversion processes, the High-purity PX PX recovery
proprietary crystallization process technology is even more economical production section section
to produce high-purity PX product at high recoveries. The process tech-
nology takes advantage of recent advances in crystallization techniques
and improvements in equipment to create this cost-effective method
for PX recovery and purification. • Compact design requires small plot size, and lowest capital
The design uses only crystallizers and centrifuges in the primary op- investment
eration. High-purity PX is produced in the front section of the process • Operation is flexible to meet market requirements for PX purity
at warm temperatures, taking advantage of the high concentration of • System is easily amenable to future requirement for incremental
PX already in the feed. At the back end of the process, high PX recovery capacity increases
is obtained by operating the crystallizers at colder temperatures. This • Feed concentration of PX is used efficiently
scheme minimizes the need for recycling excessive amounts of filtrate, • Technology is flexible to process a range of feed concentrations
thus reducing overall energy requirements. (75 wt%–95 wt% PX) using a single refrigeration system
• Design variations are used to recover paraxylene efficiently from
Process advantages: feedstocks (~22% PX) in a multi-stage system, competitive with
• High-purity PX and recovery (99.8+ wt% purity at up to 95% adsorption-based systems.
recovery)
• Crystallization equipment is simple, easy to procure and opera-
tionally trouble free
Continued 
Paraxylene, crystallization, continued
Economics: (400,000 tpy Capacity from concentrated feed)
ISBL investment cost $35 million
Paraxylene recovery 95%
Electricity consumption 50 kWh/ton PX
Operation mode Continuous
Commercial plants: Three commercial licenses.

Licensor: CrystPX is a proprietary process technology marketed and
licensed by GTC Technology Inc., in alliance with LyondellBassell
- CONTACT

Petroleum coke, naphtha,

gasoil and gas Coker gas
Application: The delayed coking technology is a thermal-cracking

process to upgrade and convert petroleum residue, asphalt, or slop Furnace Gasoline
oil into gas, naphtha, gasoil and petroleum coke. It mainly consists of
heater (furnace), coking drums, fractionating section and gas-recov- Feed Gasoil
ering section.
Description: Key points for the delayed coking technology include:

Buffer
• Premium petroleum coke (needle coke) can be produced. Naphtha
• Double-fired, multi-point steam (or water) injection, online
spalling, bi-direction steam/air decoking and other techniques Coking tower Fractionator
Coke
enable a three-year run length for the heater and 5% savings.
• The automation and safety interlock design techniques for steam
stripping, water quench, coke cooling, hydraulic decoking and
oil/gas preheating operations of the coke drums not only reduce
work intensity and ensure safe operation, but also create
conditions to reduce the drum-cycle time to 16–18 hours.
• The quench oil injection and anti-foaming agent injection with
proper position and volume control prevent foaming of the coke reduces deformation of the coke drum during oil/gas preheating
drum and fines carry-over into the fractionator. and shortens preheating time for the oil/gas.
• During the process from steam stripping to water quench, the oil • Equipment improvements of the coke drum include an overhead
vapor and steam enter a blowdown system, which treats the elliptical head instead of a spherical head, thus increasing the
vapor and steam in closed mode by stages. The blowdown effective volume of the coke drum. The transition section between
system can not only recover oil and water and reduce environ- the skirt and shell connection uses a forged piece structure instead
mental pollution, but it also can process the similar oil and waste- of overlay structure, thereby extending fatigue life. Alloy steel
water of the whole refinery. and cladding are used instead of carbon steel, thus improving
• The oil/gas preheating process of coke drum with no-coke corrosion resistance.
parking valve improves the oil/gas preheating flow scheme, • The high-efficiency internals improve separation accuracy and
enable operation flexibility; coke fine carry-over is reduced.
Continued 
Petroleum coke, naphtha, gasoil and gas, continued
• The fractionator recycle oil upper circulation washing and lower
spraying washing techniques lower coke fine carry-over in HCGO
and other products, thus improving the feed properties for down-
stream units. The low recycle-ratio operation and flexible recycle
ratio adjustment are achieved as well.
• The coke cooling water and coke cutting water are treated
separately in closed systems and recycled for reuse. All the
treated coke cooling water is recycled for reuse to protect the
environment.
• Due to large-scale unit engineering techniques, a single-unit
capacity can reach 1.4 metric tpy to 1.6 metric tpy.
Commercial plants: SINOPEC has independently designed and erected

more than 50 units with a total processing capacity of 36 million metric
tpy over the last 50 years. Thirty-three units have been designed (includ-
ing revamped units) and constructed in the last 10 years. There are four
units with a total processing capacity exceeding 1.6 million metric tpy
and are in operation. A 5.2 million metric tpy delayed coking unit is un-
der design and construction.
Licensor: China Petrochemical Technology Co., Ltd. - CONTACT

Phenol
Application: A high-yield process to produce high-purity phenol and Acetone
acetone from cumene with optional byproduct recovery of alpha meth-
ylstyrene (AMS) and acetophenone (AP). Phenol
5
Description: Cumene is oxidized (1) with air at high efficiency (+95%) 1 2 Catalyst
Air
to produce cumene hydroperoxide (CHP), which is concentrated (2) and 4 6 7 8
cleaved (3) under high-yield conditions (+99%) to phenol and acetone 3
in the presence of an acid catalyst. The cleavage mixture is neutralized
and fractionated to produce high-purity products (4–8), suitable for all Cumene
applications. AMS is hydrogenated to cumene and recycled to oxidation Hydro-
Waste oils to fuel
carbon Phenol
or optionally recovered as a pure byproduct. recovery recovery
With AMS hydrogenation, 1.31 tons of cumene will produce 1 ton Effluent Wastewater
of phenol and 0.616 tons of acetone. This high-yield process produces treatment
AMS (optional)
very high-quality phenol and acetone products with very little heavy and
light-end byproducts. With over 40 years of continuous technological
development, the Kellogg Brown & Root (KBR) phenol process features
low cumene and energy consumptions, coupled with unsurpassed safe-
ty and environmental systems.
Product quality: Typical properties of phenol product: Commercial plants: The KBR Phenol technology has been licensed to
Property Specification 25 producers, and the technology is well-proven commercially at nearly
Appearance Clear 300,000 metric tpy for single-train operations. In the last five years, KBR
Purity (dry basis), wt% 99.99 min. was awarded four grassroots phenol plants including two in China and
Total organic impurities, ppm wt < 30 two in Saudi Arabia. More than 50% of the world’s licensed phenol
Water, ppm wt < 200 capacity is produced via the KBR process.
Color (APHA) <5
Reference: Hydrocarbon Engineering, December/January 1999.
Solidification point (dry material), °C 40.85 min.
Meyers, R. A., Handbook of Petrochemical Production Processes,
Total carbonyls, ppm wt < 10
New York, McGraw Hill, 2005.
2-Methylbenzofuran (2-MBF), ppm wt <2
Sulfuric acid discoloration (SAD) test, % 95 min. Licensor: Kellogg Brown & Root LLC - CONTACT
Iron, ppm wt < 0.2

Phenol
Oxidation Decomposition Distillation
Application: The Polimeri/Lummus process is used to produce high- Spent air Acid Caustic
quality phenol and acetone products from cumene. Alphamethylstyrene Cleavage Salt
Cumene
(AMS) and pharmaceutical-grade acetone can be produced as byprod- Air
Oxidate CHP product purge
1 2 3 4 8
ucts if required.
Stripped cumene
Description: The process is based on air oxidation of cumene to cumene Fractionation feed Water
Recovered cumene
hydroperoxide (CHP) followed by acid-catalyzed decomposition of CHP Hydrogen Cumene/AMS Acetone product
to phenol and acetone. 6 5
Fresh and recycle cumene is oxidized with air to produce CHP in a Phenol and heavier
series of oxidizers (1) having a unique internal design that improves se- 7
Phenol product
lectivity and enhances safety. Oxidate is then concentrated in two evap-
Heavy waste
oration stages (2) and fed to a two-stage cleavage section (3) in which Light-waste hydrocarbons hydrocarbon
To fuel
CHP is decomposed to phenol and acetone under precisely controlled
conditions. AMS is also formed in this section from certain precursors
present in the oxidate. The cleavage section effluent is neutralized (4)
and then fractionated (5).
Acetone, cumene and AMS are taken overhead in a first distilla- environmental regulations. Polimeri’s proprietary simulation software—
tion column and pure acetone is recovered from this stream. (If desired, CheOpe Phenol—allows for the monitoring and optimization of the oxi-
acetone containing less than 50 ppm methanol can be produced for dation and cleavage sections.
pharmaceutical applications.)
Cumene/AMS are fed to a hydrogenation system (6) in which AMS Yields and product quality: The consumption of cumene (100%) per
is hydrogenated to cumene. The hydrogenated hydrocarbons are re- metric ton of phenol product is 1.308 metric ton. Phenol purity is higher
cycled to the oxidizers. than 99.99 wt% with less than 10 ppm of carbonyl impurities.
The bottoms from the first distillation column is further fraction-
Economics:
ated to reject heavies. Extractive distillation (7) using a non-aqueous
Typical utilities, per metric ton of phenol
solvent is used to separate out the carbonyl impurities, producing high-
High- and medium-pressure steam, metric ton 2.3
purity phenol.
Power, kWh 190
The technologies for both cumene oxidation and CHP decomposi-
tion minimize heavies formation and maximize conversion of by prod- Commercial Plants: The process is used in Polimeri Europa’s phenol plants
ucts into recyclable material. The process features flexible, integrated at Mantova and Porto Torres, Italy. Two licenses have been granted.
wastewater (8) and vent gas treatment systems, allowing the plant to
conform to a wide variety of local, regional, national or international Licensor: Lummus Technology - CONTACT
Phenol
Application: The Sunoco/UOP phenol process produces high-quality
phenol and acetone by liquid-phase peroxidation of cumene.
Spent air
Description: Key process steps:
Oxidation and concentration (1): Cumene is oxidized to cumene Cumene Acetone
Decomposition Phenol and
hydroperoxide (CHP). A small amount of dimethylphenylcarbinol (DMPC) Oxidation
and acetone Phenol
Air concentration
neutralization purification
is also formed, but low-pressure and low-temperature oxidation results 1
2 3
in very high selectivity of CHP. CHP is then concentrated and unreacted Residue
cumene is recycled back to the oxidation section.
H2 AMS
Decomposition and neutralization (2): CHP is decomposed to phenol hydrogenation AMS
Cumene or AMS refining
and acetone, accompanied by dehydration of DMPC to alphamethylstyrene 4
(AMS), catalyzed by mineral acid. This unique design achieves a very high
selectivity to phenol, acetone and AMS without using recycle acetone.
Decomposed catalyst is neutralized.
Phenol and acetone purification (3): Phenol and acetone are
separated and purified. A small amount of byproduct is rejected as
heavy residue.
AMS hydrogenation or AMS refining (4): AMS is hydrogenated back
to cumene and recycled to oxidation, or AMS is refined for sale. Raw materials and utilities, per metric ton of phenol
Cumene peroxidation is the preferred route to phenol, accounting Cumene, tons 1.31
for more than 90% of world production. The Sunoco/UOP Phenol process Electricity kWh 152
features low feedstock consumption (1.31 wt cumene/wt phenol). High Steam, tons 3.2
phenol and acetone product qualities are achieved through a combination Water, cooling, m3 209
of minimizing impurity formation and efficient purification techniques.
Optimized design results in low investment cost along with low utility and Commercial plants: Fourteen Sunoco/UOP Phenol process units have
chemicals consumption for low variable cost of production. No acetone been licensed with a total phenol capacity of more than 2 million metric
recycle to the decomposition section and simplified neutralization make tpy.
the Sunoco/UOP Phenol process easier to operate. Licensor: Sunoco and UOP LLC, A Honeywell Company - CONTACT
Economics: Basis: ISBL US Gulf Coast
Investment, US$/tpy (200,000 tpy of phenol) 435

Polyalkylene terephthalates— ESPREE

melt-to-resin (MTR) PIA ADD
PTA
Application: New process for directly producing polyesters from all EG
the polyalkylene terephthalate family for bottle-grade resins, based on
terephthalic acid (PTA) or dimethyl terephthalate (DMT) and diols us- M
ing the UIF proprietary two-reactor (2R) process consisting of the tow-
PM DISCAGE M
er reactor ESPREE and DISCAGE finisher without a solid-stating post-
condensation.
Description: Based on the innovative and patented design modifications Resin

to the ESPREE and DISCAGE finisher, which is provided in the medium
(MV) or high-viscosity (HV) version. Improved polymer line design, die-
face granulation, AA-conditioning, and gentle processing conditions al-
low to obtain, directly from the melt, highest viscosities of up to 1,500
Pas having a low crystallinity of less than 35% and an AA content be-
low 1 ppm without using a scavenger. The high i. V. polymer melt for
bottle-grade PET resins obtained from the DISCAGE finisher is surface Commercial plants: Five commercial units with a design capacity of
cooled and cut by an underwater granulation system in hot water. After more than 200,000 metric tpy each have been in operation since 2006.
separation of pellets and water, the resin is tempered within a few min- A pilot unit is producing 2.4 metric tpd on a semi-industrial scale.
utes at drying temperatures to avoid stickiness. Later on, the pellets are
stored for some hours in a hot air flushed silo to reduce the AA-content References: “Melt-To-Resin MTR® technology: Benefits for converters,”
to less than 1 ppm. Polyester World Congress, Zürich, 2009.
“OCTAL Petrochemicals opens the world’s largest rigid PET sheet
Economics: The solid state process (SSP) for bottle-grade resins is delet- plant,” 2009.
ed when applying this new process. The conversion costs are reduced by “Keeping ahead of the market with MTR® technology,” Creon PET
more than 28% due to lower investment, energy, labor costs and raw conference, Moscow, 2009.
material savings. Additionally, the PET resin quality is improved due to “USA: World’s First Melt-To-Resin MTR® Plant inaugurated,” 2007.
low thermal-stress treatment throughout the entire process rendering “Melt-To-Resin (MTR®). A new method to produce PET-resin eco-
the lowest polymer degradation, polydispersity, improved color and no nomically without SSP,” Int’l Fiber Journal, 2006.
core/shell viscosity structure. AA regain during preforming is minimized,
as low crystallinity requires significantly less remelting energy. Licensor: Uhde Inventa-Fischer - CONTACT

Polyalkylene terephthalates—
(PET, PBT, PTT, PEN)
Catalyst Diol Process column H2O/THF/MeOH
Application: Process to produce polyesters from the polyalkylene

terephthalate family from terephthalic acid (PTA) or dimethyl terephtha- ESPREE Diol
late (DMT) and diols using the UIF proprietary two-reactor (2R) process tower reactor
consisting of the tower reactor ESPREE and the DISCAGE finisher, for
textile applications, engineering applications or precursor. Catalyst
Description: A slurry composed of a dicarboxylic acid and a diol is pre-

M
pared at a low mole ratio. The slurry is fed to the tower reactor’s bottom
DISCAGE M Melt-phase
where the main esterification occurs under pressure or under vacuum at finisher
temperatures ranging between 170°C to 270°C. This reaction may be M I.V.: 0.55 – 1.30
PTA/diol
catalyzed or autocatalyzed. or DMT/diol M
Monomer is transferred via a pressurized pipe to the reactor top Polyesters
where reaction side products are flashed out. Higher conversion rates
(97%–99%) are achieved by a cascade of four to six reaction cups at
decreasing pressures and increasing temperatures.
Energy cost can be reduced by more than 20%. Additionally, the
Stirring and intermix are done by reaction vapors while passing
end product’s quality is improved due to eliminating intermediate prod-
through the cups. A precondensate with i.V.s of 0.28 to 0.35 is obtained
uct lines; it offers narrow residence time distribution as well as intensive
after surface-active film evaporation—done as a twin assembly, under
surface renewal and fast reaction.
vacuum and higher temperature.
The prepolymer may be finished in the melt phase with UIF’s DIS- Commercial plants: Ten commercial units with a total operating capacity
CAGE reactor. of > 3,000 metric tpd and one pilot unit of 1 metric tpd.
A process column separates side reaction low boilers from the diol,
which is then recycled back to the reaction. Spray condensers and vacu- References:“Textile polyester plant in Mogilev (Belarus) successfully put
um units recover unreacted feedstock and recycle the diol, thus improv- into operation,” 2009.
ing the economics of this process. “Vietnam: Textile Polyester plant for PVTex,” 2009.
“Germany: Uhde Inventa-Fischer technology for BASF SE,” 2008.
Economics: This new process reduces conversion cost by more than “A new highly economic Polyester Technology > 2R single-stream
25% as compared to conventional/historical processes by its compact PET process,” Chemical Fibers Int’l and Int’l Fiber Journal, 2004.
design, low energy input, short-term reaction and agitator-less design.
A product yield of more than 99.5% is attainable. Licensor: Uhde Inventa-Fischer - CONTACT

Polycaproamide Additive
preparation
Application: Uhde Inventa-Fischer’s VK-tube process polymerizes Caprolactam 2 3
M
-caprolactam (LC) monomer to produce polycaproamide (nylon-6)
chips. M
4
Description: Liquid LC is continuously polymerized in a polymerization 1
unit (one- or two-stage) (1) in the presence of water, stabilizer and mod-
ifying additives at elevated temperatures. The polymerization process
has proven to be very reliable, easy to operate and economical. Pre- 5
polymerization is available to reduce reactor volume for large capacity
units. The polycaproamide chips are formed from the melt using strand
Refeeding
pelletizing systems and are conveyed to the extraction column (2). Final PA6 chips
The chips — containing about 9% of monomer and cyclic
oligomers — are treated with hot water in the extraction column. The 6
extractables are removed, to a very large extent, to achieve a good
polymer quality and high performance when processed further.
Wet chips are sent to the centrifuge (3) and dried by hot, dry
nitrogen in a two-zone dryer (4, 5). The nitrogen gas is regenerated in
separate cycles. In the bottom zone of the dryer, the chips are cooled
via a heat exchanger. Batch and continuous process units are available to meet all potential
The drying unit can be extended to a solid-state postcondensation, requirements regarding polymer grades as well as regarding flexibility in
i.e., drying and solid-state postcondensation occurs in one process output rates and capacities. Special attention is devoted during plant
stage. Thus, high viscosity chips for industrial yarns, films and extrusion design to attain minimal operating expenses for raw material, utilities
molded parts can be produced. and personnel.
Low utility and energy consumptions are achieved by using
closed circuits of water and nitrogen as well as by recovering heat. Licensor: Uhde Inventa-Fischer - CONTACT
The recovery process for the recycling of the extractables reduces raw
material cost. Extract water is concentrated and directly re-fed (6) to
the polymerization unit.

Polyethylene Diluent recycle

Application: The Borstar polyethylene (PE) process can produce a broad Gas-phase
Prepolymerization reactor
range of bimodal and unimodal linear-low-density polyethylenes (LL- reactor
DPE), medium-density polyethylenes (MDPE) and high-density polyeth-
Catalyst Loop
ylenes (HDPE). The Borstar PE consists of a loop reactor and a gas-phase reactor Flash
reactor in series.
Product
Description: PEs with densities of 918–970 kg/m3 and melt flowrate of outlet Polymer
degassing,
0.1–100 can be produced. Ziegler Natta catalysts are used, but single- Polymer pelletizing
site catalysts will be introduced for PE processing.
Catalyst is mixed with a propane diluent and fed to the compact
prepolymerization reactor. Cocatalyst, ethylene and hydrogen are also Ethylene Ethylene
Comonomer Comonomer
fed into this reactor. The pre-polymerized slurry is sent to the loop Hydrogen Hydrogen
reactor, which is designed for supercritical conditions and operates
at 75–100°C and 55–65 bar. Typically, lower molecular weight and
higher density components of the bimodal polymers are produced in
the loop reactor. Products: A wide range of bimodal and unimodal products with a full
Diluent and unreacted components are separated from the poly- control of comonomer distribution, can be produced, with densities
mer produced in the loop reactor in a flash tank. The loop reactor ranging from 918 kg/m3 to 970 kg/m3 and melt flowrate from less
and gas-phase reactor are fully independent from each other, which than 0.1 to over 100. The MWD can be controlled from narrow to
enables easy control of reactor conditions and the flexibility to process broad. Advanced properties are tailor-made for different applications
a wide product range. such as pipe strength, film-bubble stability as well as high ESCR and
Polymer from the flash tank polymerizes further in a fluidized-bed stiffness in blow molding. Other special applications include extrusion
gas-phase reactor. No fresh catalyst is needed. The polymer contin- coating and wire and cable.
ues to grow on the same catalyst particles, resulting in a homoge-
neous polymer. The gas-phase reactor operates at 75–100°C and 20 Commercial plants: The first commercial scale Borstar PE plant is a
bar. Fresh ethylene, comonomer and hydrogen are fed into the reac- 160,000-tpy facility operating at Borealis in Finland since 1995. A retro-
tor. Typically, high molecular weight components are produced in this fitted HDPE Borstar plant at Stenungsund, Sweden, added 225,000-tpy
step, thus broadening the molecular weight distribution (MWD) and capacity in 2000. A 250,000-tpy plant started up in 2002 in China for
providing strength to the polymer. The production rate ratio between Shanghai Petrochemicals (SPC). In July 2010, Borouge, a joint-venture
the reactors can be adjusted to meet the targeted product properties. between the Abu Dhabi National Oil Co. and Borealis, formally signed
After removing hydrocarbon residuals, the polymer powder is trans-
ferred to extrusion. Continued 
Polyethylene, continued
three major engineering, procurement and construction contracts val-
ued at approximately US$ 2.6 billion for its Borouge 3 strategic expan-
sion in Ruwais, Abu Dhabi, in the UAE. The first contract worth US$
1.255 billion for the construction of two Borstar enhanced polyethylene
units and two Borstar enhanced polypropylene units, as well as the sec-
ond contract worth US$ 400 million for the construction of a 350,000
tpy low-density polyethylene (LDPE) unit. The annual capacity of the
new polyethylene units is 1.080 million tpy and the new polypropyl-
ene unit is 960,000 tpy. These significant investments will quadruple
Borouge’s production capacity to over 4.5 million tpy 2013, making it
the largest integrated polyolefins site in the world. Maximum single-line
design capacity is 350,000 tpy.
Licensor: Borealis A/S - CONTACT

Polyethylene
Application: INEOS Technologies is offering a slurry high-density polyeth-
High-pressure
ylene (HDPE) process (INNOVENE S) for license. This technology is based solvent recovery
on a process developed by Solvay. The technology was used by the BP/
Solvay joint venture in 2002 and acquired by BP when they bought out
Solvay’s share of their joint venture company in early 2005. It became
part of INEOS’s portfolio through its acquisition of Innovene at the end Catalyst
feeding system
of 2005. INNOVENE S is now the most successful HDPE technology in Low-pressure
the market with more than 2.3 million metric tons sold since this entry solvent recovery
in the licensing arena.
Monomer Monomer
Process description: The INNOVENE S process utilizes a proprietary ver- Comonomer Comonomer
tical slurry-loop reactor, as shown in the flow diagram. Two reactors Light diluent Light diluent
are used for bimodal capability. Isobutane is normally used as the hy-
drocarbon diluent in the process, although hexane may be used as an
alternative. The diluent is used as a catalyst carrier and as the polymer-
ization reactor suspension and heat transfer medium. Hexene-1 and/or
butene-1 can be used as a comonomer. Hydrogen is used for molecular
weight control when using the Zieglerg catalyst platform. Titanium-
based and chromium-based catalysts are both used. being recycled directly to the reaction system. Residual hydrocarbons
The polymerization reactor is made of large diameter pipes assem- are removed from the polymer using a countercurrent nitrogen purge
bled in a long vertical loop configuration. Early designs consisted of flow. The polymer is then pneumatically transferred to either the ex-
four- or six-leg loops. The reactor walls are made of carbon steel and truder feed tank or storage silos.
are equipped with water jackets to control temperature in the isother-
mal reactor. Ethylene is polymerized under a total pressure of about 25 Product coverage: INNOVENE S technology is capable of producing a full
bars to 40 bars and at a temperature between 75°C and 110°C (167°F MDPE/HDPE product coverage with Ziegler or chromium catalyst, using
and 230°F). The recycle diluent, fresh monomer, comonomer, hydrogen, monomodal and bimodal configuration with market leading products
catalyst and co-catalyst (when required), are fed to the reactor. Poly- such PE100.
ethylene is formed as discrete particles in a rapidly circulating diluent-
polymer slurry. On average, 98% of the ethylene is polymerized.
The concentrated withdrawn polymer slurry is flashed to separate
the powder from the diluent and unreacted monomers. The polymer
flows from the bottom of the flash tank, with the condensed overheads Continued 
High added-value products, in addition to the lowest investment
and operational costs allow INNOVENE S technology to make a winning
MDPE/HDPE business.
Reduced Processability, Matrix ESCR and creep resistance
Process advantages: impact stiffness
• Low investment costs (low equipment count) strength, Mechanical Melt strength
fumes strength during
• Operating costs extrusion
• Proven two-reactor bimodal technology
• High onstream times with no reactor fouling or cleaning
Percentage
• No wax generation and no oligomers
• Safe and environmentally clean operation
Product advantages:
• Broad MDPE and HDPE product range based
• Monomodal and biomodal capability
Molecular weight, = polymer chain length
• Chromium and Ziegler product coverage with demonstrated
catalyst transitions
• Easy product transitions
• Proprietary technology to achieve outstanding bimodal products
Properties
Licensor: INEOS Technologies - CONTACT

Polyethylene
Application: The SCLAIRTECH1 technology process produces the full
range of linear polyethylene (PE) products, including linear-low-density, Recovery and
Comonomers
medium-density and high-density grades with narrow to broad molecu- recycle
lar weight distribution. It is the most efficient PE swing process that

allows for economical production across the full spectrum of PE grades
from a single train.
Separation
Description: Ethylene and comonomer are dissolved in solvent then fed
Purification Reactor Reactor
into a reactor. Butene-1, octene-1 or both together can be used as co- feed system
monomer. The reactor system operates in a solution phase, and, due Ethylene
Extrusion
to inherent low residence time (less than 2 minutes), it offers a tremen- To finishing
dous flexibility for grade transitions and significant versatility for meet-
Pellitizer
ing product needs of a diverse market.
High conversions maximize production and eliminate any potential
for runaway reactions. A hydrocarbon solvent is used to keep the con-
tents of the reactor in solution and also aids in heat removal. The solvent
is flashed and recovered, along with the energy captured from the heat
of reaction, and circulated back to the reactor. Molten polymer is sent
to a simple extruder and pelletizer assembly. or niche applications, due to its ability to transition quickly and cov-
er a large product envelope on a single line. An ability to incorporate
Products: SCLAIRTECH process can produce PE products with density
comonomers such as octene-1 allows producers to participate in pre-
range of 0.905 – 0.965 kg/m3, melt index (MI) from 0.2 to in excess of
mium markets resulting in higher business returns.
150, and narrow to broad molecular weight distribution (MWD). This
allows producers to participate in the majority of the polyethylene mar- Commercial plants: The first SCLAIRTECH plant was built in 1960 in
ket segments including among low-, medium- and high-density films, Canada and the latest is starting-up in India in 2010. Including this new
rotational, injection and blow molding applications. facility, there are 12 plants operating worldwide with this technology,
Products made with this technology offer exceptional quality as representing 2.8 million metric tpy of total capacity.
measured by low gel, superior opticals and lot-to-lot consistency, along
with high performance characteristics for demanding applications. Licensor: NOVA Chemicals (International) S.A. - CONTACT
Economics: This technology offers advantaged economics for produc-
1
SCLAIRTECH is a trademark of NOVA Chemicals.
ers desirous of participating in a broad range of market segments and/

Polyethylene
Compressor Vent recovery
2
Application: The UNIPOL Polyethylene (PE) Process produces the widest
array of linear low-density polyethylene (LLDPE), medium-density poly- 4
ethylene (MDPE) and high-density polyethylene (HDPE) having unimodal
or bimodal molecular weight distribution (MWD) using a single, low- Catalyst
pressure, gas-phase reactor.
Purge bin
Description: The UNIPOL PE Process provides licensees proven flexibility 1 Additives
to use a single process with the capability to produce a broad product Reactor
mix that can be adapted to changing market needs. Raw materials 3
Ethylene, comonomer, hydrogen and nitrogen enter the circulation
loop that delivers reactants, cooling and mixing in a fluidized bed gas
phase reactor (1). Ziegler-Natta, chromium-based or metallocene cata- 5
lyst is fed into the reactor, which operates at low pressure (< 25 bar)
Pelletizing system To resin storage
and low temperature (approximately 90°C) and is capable of producing and loading
products with either unimodal or bimodal MWD. Adjusting and control-
ling gas composition and temperature allows for a broad product range
to be made with each catalyst. A second reaction system is not required
for bimodal products.
The reactor dome efficiently separates the solids from the circulat- where a drying gas removes the residual reactants. The mixed gas from
ing gas, and the robust design of all equipment avoids the complexity the purge bin is compressed and cooled in the vent recovery system (4)
and fouling risk of secondary separation devices such as cyclones or so condensed reactants can be easily pumped back to the reactor with-
filters. The low head compressor (2) sends the circulation gas through a out any distillation or purification. The drying and recovery is inherently
single conventional external cooler, removing the heat of reaction and simple since no diluent or solvent is used in the process.
compression. The UNIPOL PE Process pioneered the use of “Condensing In one low-investment configuration, the granular powder from the
Mode” and now “Super Condensing Mode” where a portion of the purge bin flows by gravity to the pelletizing system (5) where addi-
heavier components of the circulation are condensed and carried into tives are incorporated. Low gel pelletizing is achieved across the product
the reactor bed as well-dispersed droplets without the need for separa- slate. Univation Technologies’ attention to process design provides a
tors or pumps. The evaporative cooling allows for higher production simple and cost effective process for polyethylene manufacture.
rates and smoother operation using smaller reactors.
The product discharge system (3) uses the effect of solids displacing Products: A broad range of LLDPE, MDPE and HDPE products can be
gas to minimize reactant discharge and avoid a costly recycle compres- produced using butene or hexene comonomer with a density range of
sor. The granular PE powder is conveyed up to a settled bed purge bin Continued 
0.915 g/cm to 0.970 g/cm and a narrow, broad or bimodal MWD. Melt
index varies from less than 0.1 to greater than 200. Grades produced
are suitable for film, blow molding, pipe (PE-100), injection molding,
rotational molding and extrusion applications.
Economics: The simplicity of the UNIPOL PE Process offers low invest-

ment and operating costs while providing the flexibility to quickly adapt
product mix to changing market needs. The manufacture of bimodal
products in a single reactor reduces investment when compared against
multiple reactor processes. With a low operating pressure and no diluent
or solvent, the gas-phase process has low usage of steam and electricity,
and provides efficient use of monomer, nitrogen and water.
Commercial plants: The UNIPOL PE Process has over 40 years of proven

capability with over 100 reactor lines in operation or under construction
that range in capacity from 40 million tpy to 650 million tpy.
Licensor: Univation Technologies, LLC - CONTACT

Polyethylene, HDPE
Application: To produce high-density polyethylene (HDPE) and medi- Separation
Catalyst Polymerization Pelletizing Silo storage
um-density polyethylene (MDPE) under low-pressure slurry process— feeding and drying and packing
“CX process.” Stabilizer
Ethylene 2
Catalyst
Description: The CX process uses two polymerization reactors in se-
1 1
ries. The products have bimodal molecular-weight distribution (MWD), 3
where MWD and composition distribution is freely and easily controlled
by adjusting the operating conditions of two reactors without changing
the catalyst.
This process produces a wide melt index range by applying innova- 4
tive catalyst chemistry combined with a sophisticated polymerization
process. An all-round catalyst and simple polymerization operation pro- Solvent recovery Packing and
vide easy product changeover that reduces transition time and yields shipping
negligible off-spec product from the transition. Mitsui has also devel-
oped new catalyst that contributes better morphology of the polymer
powder and ethylene consumption.
Ethylene, hydrogen, comonomer and super-high activity catalyst are
fed into the reactors (1). Polymerization reaction occurs under a slurry
state. The automatic polymer property control system plays a very ef-
Economics: Typical consumption per metric ton of natural HDPE pellets:
fective role in product quality control. Slurry from the reactors is fed
Ethylene and comonomer, kg 1,012
to the separation system (2). The wet cake is dried into powder in the
dryer system (3). The solvent is separated from the slurry and as much
Steam, kg 305
as 90% of separated solvent is directly recycled to the reactors without
Water, cooling, ton 210
any treatment. The dry powder is pelletized in the pelletizing system (4)
along with required stabilizers. Commercial plants: Forty-six reactor lines are in operation, engineering
design or construction worldwide with a total production capacity of
Products: A broad range of homopolymer and copolymer can be pro-
over 5.8 million tpy.
duced including PE-100+ pipe grade.
Melt index 0.01 to > 50 Licensor: Mitsui Chemicals, Inc. - CONTACT
Molecular-weight distribution Freely controlled from
Comonomer distribution narrow to very wide
Density 0.93 to 0.97
Polyethylene
2
Application: The Innovene G (gas phase) process produces linear-low- Cyclone
density polyethylene (LLDPE) and high-density polyethylene (HDPE) us- 3 Exchanger
Reactor
ing Ziegler-Natta, chromium or metallocene catalysts. Polymer
finishing
1 Ethylene
Compressor
Description: Ziegler-Natta and metallocene catalysts are directly injected Comonomer
Hydrogen
into the reactor from storage where as chromium catalysts are injected 5
following activation of the catalyst via INEOS proprietary technology. The Injection
nozzle 4
INEOS catalyst portfolio enables the production of a full-range of PE prod- Separator
ucts with the same swing reactor using these three main catalyst families.
Accurate control of all product properties, such as density and melt Pump
index (MI), is achieved by continuous and automatic adjustment of the
process gas composition and operating conditions. The reactor (1) is de-
signed to ensure good mixing and a uniform temperature. Operating Economics: The low-pressure technology and ease of operation ensures that
conditions within the bed are mild; the pressure is about 20 barg, and the Innovene process is inherently safe, best-in-class environmentally and
the temperature between 75°C and 110°C. Polymer particles grow in the economically attractive with regard to both investment CAPEX and OPEX.
fluidized-bed reactor where the fluidization gas is a mixture of ethylene,
Products: A wide range of LLDPE and HDPE products can be produced
comonomer, hydrogen and nitrogen. Fine particles leaving the reactor
within the same reactor. LLDPE is used in film, injection molding and ex-
with the exit gas are collected by cyclones (2), which are unique to the
trusion applications and can be made using either butene or hexene as
Innovene gas-phase technology and recycled to the reactor. This feature
the comonomer. Narrow molecular weight HDPE provides superior injec-
ensures that fine particles do not circulate in the reaction loop, where
tion molding and rotational molding grades whereas broad molecular
they could foul the compressor, exchanger and reactor grid. The cyclones
weight HDPE is used for blow molding, pipe, film and other extrusion
also prevent product contamination during transitions. Unreacted gas
applications. mLLDPE are high peformance linear low film grade products
is cooled (3) and separated from any liquid (4), compressed (5) and re-
based on metallocene catalyst using hexene-1 or octene-1 as comono-
turned to the reactor, maintaining the growing polymer particles at the
mer. The performance of this product are key differentiator in several film
desired temperature. Catalysts are incorporated into the final product
markets segments like food packaging, lamination and stretch film.
without any catalyst removal step.
The reactor and almost all other equipment are made from carbon Commercial plants: Thirty-two licenses are operating, in design or under
steel. Polymer powder is withdrawn from the reactor via a proprietary construction worldwide representing around 8 million tpy production
lateral discharge system and separated from associated process gas in a with capacities ranging from 50,000 tpy to 450,000 tpy. Designs up to
simple degassing stage using hot recirculating nitrogen. The powder is 600,000 tpy are also available.
then pneumatically conveyed to the finishing section where additives are
incorporated before pelletization and storage. Licensor: INEOS Technologies - CONTACT
Economics: Consumption, per metric ton of PE:

Polyethylene, LDPE, autoclave reactor Ethylene, ton 1.008
Electricity, kWh 900–1,300 (homopolymer grades)
Application: The high-pressure Lupotech A autoclave reactor process
Steam, ton 0.2
is used to produce low-density polyethylene (LDPE) homopolymers,
Nitrogen, Nm3 4
EVA and various acrylic type copolymers. Single-train capacity of up
to125,000 tpy can be provided.
Description: Ethylene, initiator and, if applicable, comonomers are fed Commercial plants: Lupotech A plants with a total installed capacity of
approximately 1.5 million tpy have been licensed.
to the process and compressed to pressures up to 2,400 bar before en-
tering the autoclave reactor. Licensor: Equistar (legal entity) LyondellBasell - CONTACT
The polymer properties (MI, density, MWD) are controlled by the
initiator, pressure, temperature profile and comonomer content. After
the reactor, excess ethylene is recovered and recycled to the reactor feed
stream. The polymer melt is mixed with additives in an extruder to yield
the final product.
A range of products can be obtained using the Lupotech A process,
including standard LDPE grades to EVA copolymers or n-butyl-acrylate
modified copolymer. The products can be applied in (shrink) film extru-
sion, extrusion coating, injection molding, extrusion blow molding, pipe
extrusion, pipe coating, tapes and monofilaments.
There is no limit to the number of reactor grades that can be pro-
duced.
The product mix can be adjusted to match market demand and
economical product ranges. Advantages for the autoclave reactor de-
sign with low residence time are easy and quick transitions, startup and
shutdown.
Reactor grades from MI 0.15 to 400 and from density 0.913 to
0.932 g/cm3, with comonomer content up to 40% can be prepared.

Polyethylene, LL/MD/HDPE Recovery

Inert hydrocarbon
purge to recovery
Polymer compressor
Application: New generation Spherilene gas-phase technology with degasser Light hydrocarbons
Propane atmosphere to reactor
simplified process flow scheme, to produce the full range of linear-low- High heat transfer Fluidization
Hot spot elimination compressor
density polyethylene (LLDPE), medium-density polyethylene (MDPE) and Inherent condensation
high-density polyethylene (HDPE) The technology features process sim- Propane for Heavy hydrocarbons
On-site activation degassing to reactor
plicity, best in class monomer efficiency as well as catalyst and process Maximum shelf-life
Propane degassing
options and is able to meet all product portfolio requirements. Assured freshness
Maximized ISBL recovery
Fluidized High-monomer efficiency
Description: Solid catalyst, alkyls and donor are brought into contact in bed
reactor Excess alkyl
Catalyst Intermediate
the pre-contact vessels, where the catalyst is activated. Activated cata- unloading
neutralizer storage silo
lyst stream from the pre-contact vessel flows directly into the gas phase and dosing
reactor and is dispersed in the fluidized reacting bed. The spherical mor- From
Underwater Pneumatic
battery
phology Avant Z catalysts can be introduced directly into the reactor, limit pelletizer transport to
blending
even when empty. Chromium or other specialty catalysts are introduced Polymer purification and bagging
Raw material
when there is a seed bed in the reactor. purification
Residual HC stripping Extruder
with wet nitrogen
Ethylene, comonomer and hydrogen are fed to the reactor accord- Very low residual hydrocarbons in polymer
with excellent organoleptic properties
ing to the required production capacity and proportions needed for
the target product. Propane is used as the inert medium of reaction
and provides an independent means of controlling the reaction kinetics
while providing a heat removal capability far superior to that of inor- small amount of steam. Steam also ensures that any residual activity of
ganic inerts (such as nitrogen). The heat of the reaction is removed from catalyst system components is neutralized completely.
the fluidizing gas in a water cooled vertical heat exchanger. From the bottom of the deactivation vessel, the polymer is con-
The polymer is withdrawn continuously from a specially designed veyed pneumatically to the powder silo located on top of the extruder.
outlet at the bottom of the reactor and sent to a degassing vessel where The silo is provided with nitrogen purging to ensure that no residual hy-
monomer unreacted, comonomer and hydrogen are removed from the drocarbons accumulate in the silo. Polymer from the silos is mixed with
polymer with the help of a counter-current propane gas flow. required additives before being fed to the extruder.
The recovered gas is sent to the hydrocarbon recovery section, The Spherilene process can also be designed with two gas-phase
where the reaction components are separated from propane and both reactors in series to allow production of bimodal products. In addition,
fractions are recycled inside BL as appropriate. Thus, the hydrocarbon a Spherilene process plant built with one reactor can also be expanded
efficiency is kept very high. in the future by the addition of a second reactor circuit to increase
Polymer from the propane degassing vessel is fed by gravity to a capacity and expand product capability. Thus, Spherilene provides a
deactivation vessel where the dissolved hydrocarbons are removed from
the polymer by counter-current stripping with nitrogen assisted by a Continued 
Polyethylene, LL/MD/HDPE continued
proven and unique, future-proof technology platform to assure long
term success for a plant.
Products: Product density range is very wide, from approximately 0.915

g/cc (LLDPE) to > 960 g/cc (HDPE), including full access to the MDPE
range (0.930 to 0.940 g/cc). Melt index (MI) capability ranges from 0.01
to > 100 g/10 min. From a simple cost-effective single reactor configu-
ration, traditional LLDPE, MDPE and HDPE grades for film, blow mold-
ing, injection molding, rotomolding, geomembranes, textile, raffia and
extrusion applications, a full range of LLDPE products for cast and blown
film, extrusion coating are available. Further, the dual reactor configura-
tion enables production of premium bimodal grades (MI, density) in gas
phase with “inverse” comonomer distribution, hitherto available only
via more investment-intensive slurry technologies. Commercially proven
grades include bimodal HDPE for pressure pipe markets with PE100 cer-
tification and bimodal HDPE grades for high-strength film markets.
Economics: Consumption, per metric ton of LLDPE:

Ethylene and comonomer, ton 1.005
Steam, kg 200
Water, cooling, ∆T = 10°C, metric ton 150
Commercial plants: Licensed from 1992, 12 plants using Spherilene

process and technology have been licensed, with a total capacity of 3
million tpy. In addition, LyondellBasell operated two plants with a total
capacity of 300,000 tpy. Single-line capacities in operation range from
100,000 tpy to 370,000 tpy, with current process design available for
plants up to 600,000 tpy in single-line capacity.
Licensor: LyondellBasell - CONTACT

Polyethylene, HDPE Hexane

from
AVANT
catalyst
To monomer
recovery
tank farm
Receiver
Application: To produce bimodal and multimodal high-density polyethyl- Vent to To monomer To scrubber
ene (HDPE) using the stirred-tank, heavy-diluent Hostalen ACP process. cracker recovery Centrifuge
Catalyst
suspension
Description: The Hostalen ACP process is a slurry polymerization method vessel 4
with three reactors in series. The reaction in cascade enables producing
top quality unimodal, bimodal and multimodal polyethylene (PE) from 1 2 3 Dryer
narrow to broad molecular weight distribution (MWD) with the same Hexane 5
CW CW CW collecting 6
catalyst family. vessel
Powder
treatment 7
Polymerization occurs in a dispersing medium, such as n-hexane, Reactor Reactor Reactor vessel Nitrogen
1 2 3 Steam
using a very high-activity Ziegler catalyst. No deactivation and catalyst Hydrogen
removal is necessary because a very low level of catalyst residue remains Ethylene Powder to
Nitrogen pelletization
in the polymer. For HDPE production the catalyst, the dispersing me-
Comonomer
dium, monomer and hydrogen are fed to the reactor (1, ) where the first Co catalyst
polymerisation step occurs. Hexane to
Hexane from tankfarm mother liquor tank
The second and third step polymerization occurs under different
Hexane from
reaction conditions with respect to each reactor. No further catalyst only dryer system
ethylene, butene and further dispersing medium are fed to the second
(2) and third reactor (3). Reactor conditions are controlled continuously,
thus HDPE with very high properties is manufactured. including bimodal and multimodal molecular design. The melt flow in-
Finally, the HDPE slurry from the third reactor is sent to the decanter dex may vary from below 0.2 (multimodal product) to over 50 (unimodal
(4) and the polymer is separated from the dispersing medium. The poly- product). Homopolymers and copolymers are used in various applications
mer containing the remaining hexane is dried in a fluidized bed dryer (5) such as blow-molding (large containers, small bottles), extrusion molding
and catalyst/cocatalyst residuals are removed in the powder treatment (film, pipes, tapes and monofilaments, functional packaging), and injec-
vessel (7). tion molding (crates, waste bins, transport containers).
The powder is then pelletized in the extrusion section. The sepa-
rated and collected dispersing medium of the fluid separation step (6) Economics: Consumption, per metric ton of PE (based on given product
with the dissolved co-catalyst and comonomer is recycled to the polym- mix):
erization reactors. A small part of the dispersing medium is distilled to Ethylene and comonomer, ton 1.015
maintain the composition of the diluent. Electricity, kWh 450 including extrusion
Steam, kg 450
Products: The advanced cascade technology enables the manufacturing Water, cooling water, ∆T = 10°C, metric ton 175
of tailor-made products with a definite MWD from narrow to broad MWD, Continued 
Polyethylene, HDPE, continued
Commercial plants: There are 41 Hostalen and Hostalen ACP plants in
operation or under construction, with a total licensed capacity of 8 mil-
lion tpy. Individual capacity can range up to 400,000 tpy for a single-line
installation.

Polyethylene, LDPE, Tubular Reactor

Application: The high-pressure Lupotech T tubular reactor process is Low-pressure recycle
used to produce low-density polyethylene (LDPE) homopolymers and
EVA copolymers. Single-train capacity of up to 450,000 tpy can be pro- High-pressure recycle
vided.
Reactor
Description: Ethylene, initiator and, if applicable, comonomers are fed
to the process and compressed to pressures up to 3,100 bar before en-
tering the tubular reactor. Ethylene
The polymer properties (MI, density, MWD) are controlled by the
Comonomer
initiator, pressure, temperature profile and comonomer content. After
the reactor, excess ethylene is recovered and recycled to the reactor feed
stream. The polymer melt is mixed with additives in an extruder to yield
the final product. Extruder
A range of products can be obtained using the Lupotech T process,
including standard LDPE grades to EVA copolymers or n-butyl-acrylate
modified copolymer. The products can be applied in (shrink) film extru-
sion, injection molding, extrusion blow molding, pipe extrusion, pipe
coating, tapes and monofilaments.
There is no limit to the number of reactor grades that can be pro-
Commercial plants: Many Lupotech T plants have been installed after
duced. The product mix can be adjusted to match market demand and
the first plant in 1955, with a total licensed capacity of 9 million tons.
economical product ranges. Advantages for the tubular reactor design
LyondellBasell operates LDPE plants in Europe with a total capacity of
with low residence time are easy and quick transitions, startup and shut-
close to 1 million tpy. The newest state-of-the-art Lupotech T unit at Al-
down.
Jubail, KSA, was commissioned in 2009; with a capacity of more than
Reactor grades from MI 0.15 to 50 and from density 0.917 to 0.934
400,000 tons, it is the largest single-line LDPE plant.
g/cm3, with comonomer content up to 30% can be prepared.
Licensor: Basell Polyolefins and LyondellBasell - CONTACT
Economics: Consumption, per metric ton of PE:
Ethylene, ton 1.006
Electricity, kWh 700–900
Steam, ton –1.2 (export credit)
Nitrogen, Nm3 4

Polyethylene-LDPE
Compressor
Application: To produce low-density polyethylene (LDPE) homopolymers Modifier Cooler
comonomers
and ethylene vinyl acetate (EVA) copolymers using the high-pressure
free radical process. Large-scale tubular reactors with a capacity in the C2= Init.
Reactor
range of 130,000 tpy–425,000 tpy, as well as stirred autoclave reactors HPS
with capacity around 125,000 tpy can be used. Compressors
Description: A variety of LDPE homopolymers and copolymers can be Separators
produced on these large reactors for various applications including films,

molding and extrusion coating. The melt index, polymer density and LPS
molecular weight distribution (MWD) are controlled with temperature

profile, pressure, initiator and comonomer concentration. Autoclave re- Silo
Extruder
actors can give narrow or broad MWD, depending on the selected reac-
tor conditions, whereas tubular reactors are typically used to produce
narrow MWD polymers.
Gaseous ethylene is supplied to the battery limits and boosted to Products: Polymer density in the range 0.912 up to 0.935 for homopo-
300 bar by the primary compressor. This makeup gas, together with lymers; the melt index may be varied from 0.2 to greater than 150. Vinyl
the recycle gas stream, is compressed to reactor pressure in the second- acetate content up to 30 wt%.
ary compressor. The tubular reactors operate at pressures up to 3,000
bar, whereas autoclaves normally operate below 2,000 bar. The polymer
Economics: Raw materials and utilities, per metric ton of pelletized
polymer:
is separated in a high- and low-pressure separator; nonreacted gas is
Ethylene, ton/ton 1.007
recycled from both separators. Molten polymer from the low-pressure
separator is fed into the extruder; polymer pellets are then transferred
Steam, ton/ton 0.3
to storage silos.
Nitrogen, Nm3/t 3
The main advantages for the high-pressure process compared to
other PE processes are short residence times and the ability to switch Commercial plants: Affiliates of ExxonMobil Chemical Technology Licens-
from homopolymers to copolymers incorporating polar comonomers ing LLC operate 18 high-pressure reactors on a worldwide basis with a
in the same reactor. The high-pressure process produces long-chain, capacity of approximately 1.75 million tpy. Homopolymers and a variety
branched products from ethylene without expensive comonomers that of copolymers are produced. Since 1996, ExxonMobil’s LDPE process has
are required by other processes to reduce product density. Also, the been licensed to 10 licensees with a total installed capacity (either in op-
high-pressure process allows fast and efficient transition for a broad eration or under construction) of approximately 1.9 million tpy.
range of polymers.
Licensor: ExxonMobil Chemical Technology Licensing LLC - CONTACT
Polypropylene
Application: The Borstar polypropylene (PP) process can produce ho- Gas-phase 1st Rubber 2nd Rubber
reactor gas-phase gas-phase
mopolymers, random copolymers, heterophasic copolymers, and very reactor reactor
high-rubber-content heterophasic copolymers. It is a modular process; (optional) (optional)
consisting of a loop reactor/gas-phase reactor combination. Catalyst

Loop
reactor
Description: PP with a melt flowrate ranging from 0.1 to 1,200 can be
produced. Borstar PP uses a Ziegler Natta catalyst, but single-site cata- Polymer
degassing
lysts can be used in the future. When producing homopolymers and pelletizing
random copolymers, the process consists of a loop reactor and a gas-
phase reactor in series. One or two gas-phase reactors are combined to Propylene
Comonomer
manufacture heterophasic copolymers. Hydrogen Propylene Propylene Propylene
Comonomer Comonomer Comonomer
Propylene, catalyst, cocatalyst, donor, hydrogen, and comonomer Hydrogen Hydrogen Hydrogen
(for random copolymers) are fed into the loop reactor; propylene is used Homo and random Heterophasic Advanced heterophasic
copolymers copolymers copolymers
as the polymerization medium (bulk polymerization). The loop reactor
is designed for supercritical conditions and operates at 80–100°C and
50–60 bar. The propylene/polymer mixture exits the loop reactor and
is sent to a fluidized-bed, gas-phase reactor, where propylene is con-
sumed in polymerization. This reactor operates at 80–100°C and
25–35 bar. Fresh propylene, hydrogen and comonomer (in case of ran-
Products: A wide range of polypropylenes with varying melt flowrates
dom copolymers) are fed into the reactor. After removing hydrocarbon
from 0.1 to 1,200, and from very stiff to very soft polymers are pro-
residuals, the polymer powder is transferred to extrusion.
duced and can be tailored to customer needs. The products have reac-
For heterophasic copolymers, polymer from the gas-phase reactor
tor-made basic properties, thus minimizing additional compounding or
is transferred to another, smaller gas-phase reactor where the rubbery
other post-reactor treatment. Grades suitable for molding, film, fiber,
copolymer is made. After this processing step, hydrocarbon residuals
thermoforming and pipe, as well as for engineering applications, are
are removed, and the powder is transferred for extrusion.
produced.
The basic module, loop/gas-phase reactor combination, enables
high once-through conversion (minimized recycle), since unreacted Commercial plants: The first Borstar PP plant has successfully operat-
monomer from loop reactor is consumed in the gas-phase reactor. Po- ed since May 2000 in Schwechat, Austria, with 200,000-tpy capacity.
lymerization conditions in each reactor can be independently controlled, Maximum single-line design capacity can achieve 400,000 tpy. In July
enabling production of both standard unimodal and broad-molecular- 2010, Borouge, a joint-venture between the Abu Dhabi National Oil
weight multimodal grades. The production rate ratio between the reac-
tors can be adjusted to meet the targeted product properties. Continued 
Polypropylene, continued
Co. and Borealis, formally signed three major engineering, procure-
ment and construction contracts valued at approximately US$ 2.6 bil-
lion for its Borouge 3 strategic expansion in Ruwais, Abu Dhabi, in the
UAE. The first contract worth US$ 1.255 billion for the construction of
two Borstar enhanced polyethylene units and two Borstar enhanced
polypropylene units, as well as the second contract worth US$ 400
million for the construction of a 350,000 tpy low-density polyethylene
(LDPE) unit. The annual capacity of the new polyethylene units is 1.080
million tpy and the new polypropylene unit is 960,000 tpy. These sig-
nificant investments will quadruple Borouge’s production capacity to
over 4.5 million tpy 2013, making it the largest integrated polyolefins
site in the world.
Licensor: Borealis A/S - CONTACT

Polypropylene
Application: To produce homopolymer, random copolymer and impact
copolymer polypropylene using the Dow gas-phase UNIPOL PP process.
2 6
Description: A wide range of polypropylene is made in a gas-phase, flu-
idized-bed reactor using proprietary catalysts. Melt index, isotactic level 3
7
and molecular weight distribution are controlled by utilizing the proper Catalyst
1 5
catalyst, adjusting operating conditions and adding molecular-weight 4 8
control agents. Random copolymers are produced by adding ethylene
or butene to the reactor. Ethylene addition to a second reactor in series
is used to produce the rubber phase of impact copolymers.
Polypropylene to
The UNIPOL PP process’ simple yet capable design results in low Propylene resin loading
investment and operating costs, low environmental impact, minimal po- comonomers 9
tential fire and explosion hazards, and easy operation and maintenance.
To produce homopolymers and random copolymers, gaseous propylene,
comonomer and catalyst are fed to a reactor (1) containing a fluidized-
bed of growing polymer particles and operating near 35 kg/cm2 and ap-
proximately 70°C. A conventional, single-stage, centrifugal compressor
(2) circulates the reaction gas, which fluidizes the reaction bed, provides
raw materials for the polymerization reaction and removes the heat of Hydrocarbons remaining in the product are removed by purging with ni-
the reaction from the bed. Circulating gas is cooled in a conventional trogen. Granular products are pelletized in systems available from mul-
heat exchanger (3). Granular product flows intermittently into product tiple vendors (9). Dow has ongoing development programs with these
discharge tanks (4); unreacted gas is separated from the product and suppliers to optimize their systems for UNIPOL PP resins, guaranteeing
returned to the reactor. low energy input and high product quality. Controlled rheology, high
To make impact copolymers, the polypropylene resin formed in the melt-flow grades are produced in the pelleting system through the ad-
first reactor (1) is transferred into the second reactor (5). Gaseous pro- dition of selected peroxides.
pylene and ethylene, with no additional catalyst, are fed into the sec-
ond reactor to produce the polymeric rubber phase within the existing Products: Homopolymers can be produced with melt flows from less
polypropylene particles. The second reactor operates in the same man- than 0.1 to 3,000 dg/min and isotactic content in excess of 99%. Ran-
ner as the initial reactor, but at approximately half the pressure, with a dom copolymers can be produced with up to 12 wt% ethylene or up to
centrifugal compressor (6) circulating gas through a heat exchanger (7) 21 wt% butene over a wide melt flow range (< 0.1 to > 100 dg/min).
and back to the fluid-bed reactor. Polypropylene product is removed by
product discharge tanks (8) and unreacted gas is returned to the reactor. Continued 
A full range of impact copolymers can be polymerized with excellent
stiffness for even the most demanding applications. Products from nar-
row to broad molecular-weight distribution can be manufactured in
grades with proven advantage for film injection, molding, blow mold-
ing, extrusion and textile applications.
Proprietary catalyst and donor systems: The Dow Chemical Co. manu-
factures and provides a family of polypropylene catalysts (SHAC catalyst)
and a family of external electron donors (SHAC ADT) for use in the
UNIPOL PP process. SHAC catalyst offers high catalyst activity (up to 35
kg/g-hr using conventional external donor and up to 60 kg/g-hr using
a SHAC ADT) and competitive polymer properties. SHAC ADT performs
three functions:
1) Controlling polymer isoctaticity similar to conventional external
donors, such as D donor or C donor
2) Further improving process continuity by preventing agglomera-
tion of polymer particles
3) Enhancing polymer properties.
The combination of SHAC catalyst and SHAC ADT enables Dow’s
catalyst systems to achieve low cost and easy production of polypropyl-
ene polymer with superior properties. The exceptional performance of
the SHAC catalyst systems also finds applications in other PP processes.
Commercial plants: Nearly 45 reaction lines are in operation, with ca-

pacities ranging from 80,000 tpy to 650,000 tpy. Approximately seven
additional plants are in design and construction. UNIPOL PP offers single-
reaction-line systems capable of producing the full range of PP products
at capacities up to 650,000 tpy. Total worldwide licensed production of
polypropylene with this technology is nearly 12 million tpy.
Licensor: The Dow Chemical Co. Univation Technologies is the licensor

of the UNIPOL PP process. - CONTACT

Polypropylene
Applications: To produce the full range of polypropylene (PP), including
homopolymer, random copolymer and impact copolymer PP, using the CW
ExxonMobil PP Process. 3
Description: The ExxonMobil PP process utilizes series, bulk-liquid loop

reactors (1) for the production of homopolymer and random copolymer Propylene 1 1 2
PP, plus a gas phase reactor (2) in combination with the loop reactors CW
Catalyst
to production impact copolymer PP. The use of series loop reactors al-
lows the production of different products, as necessary, in each reactor
4
to tailor the final product properties for specific end-use applications.
Advancements in the design, chemistry and operation of the gas-phase
reactor, in combination with ExxonMobil proprietary catalyst system
Ethylene
technology, allows the production of impact copolymer PP with industry Pellets
leading impact/stiffness balance properties with excellent operational
reliability. Additionally, the design allows production of impact copo-
lymer PP with a broad range of impact resistance, including very high-
impact resistance grades in a single gas-phase reactor.
The ExxonMobil PP Process has been demonstrated to handle PP granules plus the final product additive package are finished in
a wide range of supported catalyst solids, which permits the manu- a twin screw extrusion system (4) including any post-reactor modifica-
facturer to select a catalyst solid that delivers the optimum in product tion of the polymer molecular weight and molecular weight distribution
performance and economics. required by the specific product application, typically referred to as con-
A unique feature of the ExxonMobil PP Process is the monomer trolled rheology (CR) technology.
recovery system (3) that utilizes indirect heating and residence time to
remove the remaining unreacted monomer without exposing the gran- Products: The ExxonMobil commercial grade slate covers a wide range
ules directly to a large steam flow. The result is no mixing of hydrocar- of homopolymer, random copolymer and impact copolymer PP for vol-
bon and steam, which then requires additional equipment for separa- ume and specialty applications. ExxonMobil PP products are known for
tion and recovery of the hydrocarbon. This approach lowers the capital their quality and lot-to-lot consistency. Key consumers of PP products
investment as well as significantly reducing steam and electricity con- consider ExxonMobil PP products to be the industry’s leader in many im-
sumption vs. other PP technologies. portant applications including OPP film; nonwoven fiber; durable goods
The ExxonMobil PP process lines are in operation using both including automotive and appliance applications; consumer products;
chemical-grade and polymerization-grade propylene as feed. rigid packaging; and materials handling applications.
Continued 
Economics: Typical consumption per metric ton of PP:
Polymerization Finishing
Homopolymer Copolymer
Electricity, kWh 50–60 70–80 150–200
Steam, kg 160 130 25
Water, cooling m3 60 80 40
Commercial plants: Four lines are in operation, with a fifth line to be

completed in 2010. Two of the four operating lines have a capacity of
more than 400,000 tpy. The fifth line will have a capacity in excess of
450,000 tpy. Single train lines with a capacity of 600,000+ tpy have
been designed and are available for license.
Licensor: ExxonMobil Chemical Technology Licensing LLC - CONTACT

Polypropylene
Cocatalyst 2
Application: To produce polypropylene (PP) homopolymer, random co- Condenser Propylene recycle to reactor
polymer and impact copolymer using the Innovene PP gas-phase pro- Modifier
cess with proprietary 4th generation supported catalyst. Catalyst CW Propylene Powder/gas
5 separation
Propylene
Description: Catalyst in mineral-oil-slurry is metered into the reactor to- Reactor #1
recovery
1 fuel
gether with co-catalyst and modifier. The proprietary supported catalyst first polymerization or flare
Power
developed by INEOS has controlled morphology, super-high activity and 2 deactivation
Reactor Condenser 6
very high sterospecifity. The resulting PP product is characterized by nar- powder Moist nitrogen
row particle size distribution, good powder flowability, minimum cata- transfer 3
system CW Propylene
lyst residues, noncorrosiveness, excellent color and low odor. Additives
The horizontal stirred-bed reactor (1) is unique in the industry in that 4
Ethylene
it approaches plug-flow type of performance, which contributes to two Reactor #2
major advantages. First, it minimizes catalyst bypassing, which enables the second polymerization Pelletized product
7
process to produce very high-performance impact copolymer. Second, it
makes product transitions very quick and sharp, which minimizes off-spec
transition materials. The reactor is not a fluidized bed, and powder mixing
is accomplished by very mild agitation provided by a proprietary-designed
horizontal agitator. Monomer leaving the reactor is partially condensed column (6) for catalyst deactivation. The deactivated powder is then
(2) and recycled. The condensed liquid together with fresh makeup pelletized (7) with additives into the final products.
monomer is sprayed onto the stirred reactor powder bed to provide
Products: A wide range of polypropylene products (homopolymer, ran-
evaporative cooling (remove the heat of polymerization) and control the
dom copolymer and impact copolymer) can be produced to serve many
bed temperature. Uncondensed gas is returned to the reactor.
applications, including injection molding, blow molding, thermoform-
For impact copolymer production, a second reactor (4) in series is
ing, film, extrusion, sheet and fiber. Impact copolymer produced using
required. A reliable and effective gas-lock system (3) transfers powder
this process exhibits a superior balance of stiffness and impact resistance
from the first (homopolymer) reactor to the second (copolymer) reactor,
over a broad temperature range.
and prevents cross contamination of reactants between reactors.
This is critically important when producing the highest quality impact Commercial plants: Twenty-two plants are either in operation or in de-
copolymer. In most respects, the operation of the second reactor system sign/construction worldwide with capacities ranging from 65,000 to
is similar to that of the first, except that ethylene in addition to propylene 450,000 metric tpy.
is fed to the second reactor. Powder from the reactor is transferred and
depressurized in a gas/powder separation system (5) and into a purge Licensor: INEOS Technologies - CONTACT

Polypropylene
Application: A process to produce homopolymer polypropylene and Cocatalyst
Propylene recycle/recovery
ethylene-propylene random and impact co-polymers Japan Polypropyl- Propylene
ene Corp. (JPP) HORIZONE Technology (formerly known as Chisso Gas- Powder/gas
Catalyst
Phase Technology) utilizing horizontal plug-flow reactor. 4 separation
Propylene
Description: The process features a horizontal agitated reactor and a Reactor (1)
recovery
high-performance catalyst specifically developed by the licensor. The
Gas Purge
catalyst has a controlled morphology, very high activity and very high 5 column
lock
selectivity. The process provides low energy consumption, superior Ethylene, 2 Moist nitrogen
ethylene-propylene impact co-polymer properties; minimum transition propylene
products, high polymer throughput and a high operating factor. Each Additives
process step has been simplified; consequently, the technology offers
Reactor (3) 6 Pelletized
a low initial capital investment and reduced manufacturing costs while product
providing product uniformity, excellent quality control and wide range
of polymer design, especially for comonomer products.
Particles of polypropylene are continuously formed at low pressure
in the reactor (1) in the presence of catalyst. Evaporated monomer
is partially condensed and recycled. The liquid monomer with fresh
propylene is sprayed onto the stirred powder bed to provide evapora-
Commercial plants: Eleven polypropylene plants are in operation or un-
tive cooling. The powder is passed through a gas-lock system (2) to
der construction, with capacities ranging from 65,000 tpy to 300,000
a second reactor (3). This acts in a similar manner to the first, except
tpy. JPP offers processing designs for single-production with capacities
that ethylene as well as propylene is fed to the system for impact co-
reaching 400,000 tpy.
polymer production. The horizontal reactor makes the powder resi-
dence time distribution approach that of plug-flow. The narrowness of Licensor: Japan Polypropylene Corp. (JPP) - CONTACT
residence time distribution contributes to higher product quality. The rights to license this technology were given from Chisso to Ja-
The powder is released periodically to a gas-powder separation system pan Polypropylene Corp., which is a PP joint venture between Chisso
(4). It is depressurized to a purge column (5) where moist nitrogen deac- and Mitsubishi Chemical Corp.
tivates the catalyst and removes any remaining monomer. The monomer
is concentrated and recovered. The powder is converted into a variety of
pelletized resins (6) tailored for specific market applications.

Polypropylene
Application: To produce polypropylene (PP) including homopolymer, Polymerization Polymerization Drying Silo storage
random copolymer and impact copolymer. (homo/random) (copolymer) and packing
Stabilizer
Ethylene
Description: The process, with a combination of the most advanced
Propylene
high-yield and high-stereospecificity catalyst, is a nonsolvent, non-
Cocatalyst 4
deashing process. It eliminates atactic polymers and catalyst residue 2
removal. The process can produce various grades of PP with outstand- Catalyst
ing product quality. Polymer yields of 20,000 kg/kg to 100,000 kg/ 1
3
kg of supported catalyst are obtained, and the total isotactic index of 5
polymer can reach 98% to 99%.
With new catalysts based on di-ether technology (fifth-generation Packing and
shipping
catalyst, RK-Catalyst and RH-Catalyst), the process can produce wider
melt index ranged polymers due to the high hydrogen response of RK/
RH-Catalyst.
The reactor polymer has narrow and controlled particle size distri-
bution that stabilizes plant operation and also permits easy shipment
as powder. Due to the proprietary design of gas-phase reactor, no Products: The process can produce a broad range of polypropylene poly-
fouling is observed during the operation, and, consequently, reactor mers, including homopolymer, random copolymer and impact copolymer,
cleaning after producing impact copolymer is not required. In addi- which become high-quality grades that can cover various applications.
tion, the combination of the flexibility of the gas-phase reactor and
high-performance catalysts allow processing impact copolymer with Economics: Typical consumption per metric ton of natural propylene
high ethylene content. homopolymer pellets:
In the process, homopolymer and random copolymer polymeriza- Propylene (and ethylene for copolymer), kg 1,005
tion occurs in the loop-type reactor (1). For impact copolymer produc- Electricity, kWh 320
tion, copolymerization is performed in a gas-phase reactor (2) after Steam, kg 310
homopolymerization. The polymer is discharged from a gas-phase Water, cooling, t 100
reactor and transferred to the separator (3). Unreacted gas accom- Commercial plants: Twenty-seven reactor lines are in operation, engi-
panying the polymer is removed by the separator and recycled to the neering design or under construction worldwide, with a total produc-
reactor system. The polymer powder is then transferred to the dryer tion capacity of over 3.4 million tpy.
system (4) where remaining propylene is removed and recovered. The
dry powder is pelletized by the pelletizing system (5) along with re- Licensor: Mitsui Chemicals, Inc. - CONTACT
quired stabilizers.
Polypropylene
Application: To produce polypropylene (PP) homopolymer, random co- Catalyst
polymers and impact copolymers, including Metallocene PP in the No- Co-catalyst
stereomodifier
volen process.
Recycle gas Recycle gas
condenser compressor Gas/solids
Description: In the Novolen process, polymerization is conducted in separation
one or two gas-phase reactors, (1) and (2). The reactors contain a 2nd
3
unit
1 reactor 2
bed of polypropylene powder, which is agitated below the fluidiza- Nitrogen
1st
tion point by a helical agitator to keep the bed in motion and prevent Recycle reactor Solid Peroxide
pump
powder agglomeration. A wide range of products can be produced add- Pellets
itives Molten to silo
with, at most, two reactors connected in series, including super-high- M M additives farm
impact copolymers. The second reactor is used either to incorporate Propylene Propylene Recycle
gas cooler
rubber into the homopolymer matrix produced in the first reactor, or Comonomer
Comonomer
the reactors are configured in parallel while producing homopolymers Hydrogen Extruder Die-face
Hydrogen 4
or random copolymers at capacities up to 600,000 metric tpy. It is cutter
also possible to switch between parallel and cascade mode in one
line—Versatile Reactor Concept (VRC)—providing great flexibility with
respect to capacities and product production capability.
Polymerization heat is removed from the reactors by external cooling
circuits. Polymer powder is continually withdrawn from the reactors.
Commercial plants: The capacities range from 60,000 to 450,000 met-
The powder transfer from the first to the second reactor and from the
ric tpy for single lines. Over 50 production lines are in operation, engi-
second reactor to the gas/solids separation unit (3) is pressure driven.
neering or under construction. The total licensed capacity worldwide for
In this gas/solids separation unit polymer powder is separated from
the Novolen process is in excess of 8 million tons.
unreacted monomer and directly fed to the extruder (4) for pelletizing.
The unreacted monomer is recovered and recycled. Removal of catalyst Licensor: Lummus Novolen Technology GmbH - CONTACT
residues or amorphous polymer is not required.
Products: The process can produce a wide variety of homopolymers,

random copolymers including terpolymers and pentene copolymers,
and impact copolymers with up to 50% rubber content. Product range
also includes metallocene PP based on a simple drop-in technology.

Commercial plants: Metocene polypropylene technology is applied

Polypropylene, Metallocene upgrade worldwide in the developed polymers markets, i.e., Europe, US and
Asia. At present, Metocene technology has been implemented into five
Application: Metocene polypropylene (PP) technology upgrades exist-
Spheripol plants and one gas plant. The current capacity of the PP plants
ing and newly built PP plants by extending plant capability to cover
upgraded with Metocene range between 60,000 tpy and 220,000 tpy.
specialty PP products with specific and unique features that can be pro-
duced with single-site catalysis, in addition to the existing conventional Licensor: LyondellBasell - CONTACT
product portfolio.
Description: Metocene PP technology can be implemented to PP pro-

cesses where polymerization takes place in either liquid phase, including
such as Spheripol, or in gas phase. The retrofit required for implement-
ing Metocene technology into Spheripol plants and other PP process
technologies is dependent on the specific plant design. It relates to ad-
aptations of the plant to specific requirements of such single-site cataly-
sis and related PP products. Plants that have implemented Metocene
technology can continue to produce conventional PP products based
on Ziegler-Natta catalysts in addition to Metocene-based operation
with metallocene-based catalysts. The addressable portfolio of specialty
products covers all typical product fields, i.e. propylene homo-polymers
and propylene co-polymers.
Products: The main driver of Metocene implementation is the desire to

generate differentiated products with new and/or improved properties.
Major property highlights of Metocene-based PP products include: high
purity, high uniformity, high transparency, in addition to a broad range of
peroxide-free reactor grades including very high melt-flow grades, and
special suitability for high-performance processing in injection molding
and fiber spinning.

Polypropylene
Application: Spheripol process technology produces propylene-based
polymers including homopolymer polypropylene (PP) and many families
of random and heterophasic impact and specialty impact copolymers. 2
CW 4
Description: In the Spheripol process, homopolymer and random copo-
lymer polymerization takes place in liquid propylene within one or two Catalyst Steam
1
tubular loop reactors (1) in cascade. Heterophasic impact copolymeriza- 3
tion can be achieved by adding a gas-phase reactor (3) in series.
Unreacted monomer is flashed in a two-stage pressure system (2, Propylene 5
4) and recycled back to the reactors mostly by condensation with CW
and pumping. This improves yield and minimizes energy consumption.
Steam
Dissolved monomer is removed from the polymer by a steam sparge
Ethylene Polymer
(5). The process can use lower-assay chemical-grade propylene (93% to to storage
95%) or the typical polymerization-grade (99.5%).
Yields: Polymer yields of 40,000–60,000 kg / kg of supported catalyst

are obtained. The polymer has a controlled particle size distribution and
an isotactic index of 90%–99%.
Economics: The Spheripol process offers a broad range of products with copolymers (up to 25% bonded ethylene), as well as high-stiffness and
excellent quality and low-capital and operating costs. high-clarity copolymers.
Consumption, per metric ton of PP (polymerization): Commercial plants: Spheripol technology is used for about 40% of the
Propylene and comonomer, ton 1.001 total global PP capacity. There are more than 100 Spheripol process
Catalyst, kg 0.016–0.025 plants licensed or operating worldwide with total capacity of about
Electricity, kWh 80* 21 million tpy. Single-line design capacity is available in a range from
Steam, kg 280 40,000 tpy to 550,000 tpy.
Water, cooling, metric ton 90
Products: The process can produce a broad range of propylene-based *
In case of copolymer production, an additional 20 kWh is required.
polymers, including homopolymer PP, various families of random copo-
lymers and terpolymers, heterophasic impact and speciality impact

Polypropylene
Application: To produce polypropylene-based polymers, including ho-
mopolymer polypropylene (PP), random, heterophasic impact and spe-
cialty dual composition copolymers, using Spherizone process technol- Barrier
sections
ogy.
Description: The Spherizone process is LyondellBasell’s new proprietary

gas-loop reactor technology based on a Multi-Zone Circulating Reactor Multi-zone
circulating C3 feed
(MZCR) concept. Inside the reactor (1) the growing polymeric granule is reactor
Steam
continuously recirculating between two interrelated zones, where two Gas-phase
reactor
distinct and different fluodynamic regimes are realized.
In the first zone (1a), the polymer is kept in a fast fluidization regime;
Catalyst
when leaving this zone, the gas is separated and the polymer crosses
the second zone (1b) in a packed-bed mode and is then reintroduced Nitrogen
in the first zone. A complete and massive solid re-circulation is obtained Propylene + hydrogen
Propylene +
To polymer
hydrogen
between the two zones. Ethylene handling
Ethylene and extrusion
The gas composition with respect to the chain terminator (hydro-
gen) and to the comonomer can be altered between the two zones of
the MZCR. This is accomplished by injecting monomers from the exter-
nal system (2) in one or more points of the second zone (1b) and so two lyst deactivation (6). The removed residual hydrocarbons are recycled
or more different polymers (MFR and/or comonomer type and content) to the reaction. While the polymer is dried by a closed-loop nitrogen
can grow on the same granule. system (7) and, now free from volatile substances, the polymer is sent
While the granules recycle through the multiple zones, different to additives incorporation step (8).
polymers are generated in an alternate and cyclic way via continuous po-
lymerization. This allows the most intimate mixing of different polymers, Economics: Raw material and utility requirements per metric ton of
giving a superior homogeneity of the final product. Unreacted monomer product (polymerization):
is mostly recovered at intermediate pressure (3) and recycled back to the Propylene (and comonomer for copolymers), kg 1,001
MZC reactor through a compressor, while polymer can be fed to a fluid- Catalyst, kg 0.025
ized gas- phase reactor (4) operated in series (optional) where additional Electricity, kWh 120*
copolymer can be added to the product from the gas loop. Steam, kg 120
From the intermediate separator/second reactor, the polymer is dis- Water, cooling, m3 85
charged to a receiver (5), the unreacted gas is recovered, while the poly-
mer is sent to a proprietary unit for monomer steam stripping and cata- Continued 
Products: The process can produce a broad range of propylene-based
polymers, including mono- and bimodal (medium/wide/very wide molec-
ular weight distribution) homopolymer PP, high stiffness homopolymers,
random copolymers and terpolymers, high-clarity random copolymers as
well as two compositions copolymer/random copolymer, twin-random
or random/heterophasic copolymer). Conventional heterophasic impact
copolymers (with improved stiffness/impact balance) can be produced
with the second additional gas phase reactor, with ethylene/ propylene
rubber content up to 40%.
Commercial plants: A retrofitted 160,000 tpy plant is in operation at

the LyondellBasell site in Brindisi since 2002, and 10 licenses for a total
capacity of 3.25 million ton have been granted since 2004. The larg-
est unit licenses are two 450,000-tpy single-line plants operating since
2009 and 2010 respectively.
*In case of high impact copolymer production, an additional 20 kWh is required.

Polystyrene
Application: The INEOS polystyrene (PS) technology is based on a bulk Styrene Preheater
continuous process giving access to a wide range of general purpose Styrene recycle
Rubber
polystyrene (GPPS) also known as crystal polystyrene and high-impact grinder 3
polystyrene (HIPS), which incorporates rubber particles for high shock Polymerization
reactor
absorbance. Dissolver
Feed
storage Prepoly
1 2 reactor 5
Products and economics: The process yields a variety of superior prod- 4 8
ucts with attractive investment and conversion costs. These products Recovery
6
are sold and well accepted worldwide. INEOS offers commercially prov- Preheater column
en swing-line technology, capable of producing both GPPS and HIPS Devol

grades, with capacities ranging from 60,000 tpy up to 200,000 tpy that 7
provide a turndown capability of 60%. Storage Pelletizer Die head

10 9
Description: The INEOS PS technology can be divided into several key
processing operations as follows:
Rubber dissolving (1): Polybutadiene rubber, in bale form, is
chopped into crumbs. To enhance dissolving, preheated styrene is intro-
duced into a high-shear in-line mixer. This operation allows high capac-
ity production of dissolved rubber at a high rubber concentration.
second stage. The stripping effect of the foaming agent reduces the
Prepolymerization (4): Prepolymerization is conducted in the first
residual monomer content to as low as 200 ppm.
two reactors that are CSTR-type with proprietary agitator designs. Pre-
Recycle recovery (8): Unreacted styrene and diluents from the de-
polymerization may be thermally or chemically initiated depending on
volatilization operation are distilled and recycled to the front end of the
the desired product. For HIPS, this is a critical phase of the process since
process. The distillation of the recycle stream ensures that only styrene
this is where the rubber morphology and physical properties of the re-
and ethylbenzene are recycled back to the first pre-polymerization reac-
sultant product are controlled.
tor to ensure that the styrene purge is minimized and the oligomer con-
Polymerization (5): Polymerization is conducted in the last reactor,
centration in the reactor system is kept low. Two purges are provided
which is a plug-flow type of proprietary design allowing high efficiency
to control the accumulation of light and heavy components in the PS
heat removal and temperature control on viscous media.
unit: a lights purge consisting of styrene and ethylbenzene and a heavy
Devolatilization (7): This is a two-step operation under high vac-
purge consisting of oligomers and other heavy organics. These purges
uum, to remove lights components such as unreacted styrene and di-
are used as fuel for the hot oil heater.
luent, which is enhanced with the addition of a foaming agent in the
Continued 
Polystyrene, continued
Finishing: This section consists of filtering the polymer melt, ex-
truding it into strands, cutting them into cylindrical pellets of prescribed
size, sorting the resultant pellets from fines and oversize pellets and
conveying the product pellets to a quality control silo.
Process features:
• Proprietary rubber grinding and dissolving unit
• Catalyzed polymerization:
o Enhanced polymer/rubber grafting
o Reduced oligomers byproducts
• Proven proprietary prepoly reactor design allowing temperature
and morphology control
• Proprietary plug-flow reactor design => outstanding temperature
control, highest conversion rates, rubber morphology preservation
• High-efficiency devolatilization system
• LP steam generation system
• Ongoing development of new and improved formulations.
Client benefits:
• High rubber efficiency
• Low-investment cost and inventory on the rubber section
• Excellent rubber yields
• High consistency and high product quality thanks to rubber
morphology control
• Minimized capital investment
• High reliability
• Best in class residual SM on final product
• Fast transitions, high prime quality yields
• Consistent, high quality products
• Lowest utility consumption among licensed technologies
• Market penetration into new applications.
Commercial plants: At present, nearly 1.3 million metric tpy world-scale

capacities have been awarded through seven different projects using
INEOS proprietary technology.

Polystyrene, expandable
Application: For the production of regular and flame-retardant expand- Initiator and
chemical additives
Suspending agents
and water
Clean air
able polystyrene, INEOS offers the “one-step” suspension process.

Styrene Optional: Pentane
recovery package
Products and economics: This state-of-the-art technology offers a wide
range of products with an attractive capital investment and operational Centrifuge Pentane recycling
costs. Computer control and monitoring ensure consistent products Water
Dryer
Reactor 1 3 Screening
with capacity up to 100,000 tpy per line.
Effluent 5
4
treatment
Description: Depending on the formulation, styrene, blowing agent, Blender
Additives
water, initiators, suspending agents and other additives are injected into Slurry 6
tank 2
the reactor (1). The reactor contents are then subjected to a time-tem-
perature profile under agitation. The combination of suspending agent
Air Air
and agitation disperse the monomer to form beads. Polymerization is Up to 4 reactors To product
Batch Intermediate
then continued to essentially 100% conversion. This unit operation is Continuous storage hoppers packaging
fully DCS controlled through an automated sequence. After cooling, the

polystyrene beads and water are discharged to a slurry tank (2).
The downstream slurry tank process becomes fully continuous. The
bead/water slurry is centrifuged (3) so that most of the “suspension
water” is removed. The beads are conveyed to a pneumatic-type flash • Narrow-bead size distribution thanks to the mineral suspension
dryer (4) where surface moisture is removed. system
The dry beads are then screened (5) yielding two targeted product • High reactor productivity/high capacity design (up to 100,000
cuts out of four possible options. Such segregation is achievable thanks metric tpy on a single line)
to the mineral suspension, which increases the yield for a targeted cut. • Proven and easy to operate technology
With organic suspensions, the four product cuts are produced at the • Optional volatile organic compound (VOC) recovery system
same time. Fig. 2 shows the effects of mineral vs. organic suspension in • The process includes batch reactions automatically controlled
terms of product size distribution. Narrower distributions allow target- followed by a fully continuous downstream section
ing more specifically product cut in line with market needs. Typically, the • Continuous low residence time coating process.
fine to medium cuts target the packaging market, whereas the medium Market advantages:
to big cuts target the insulation market. • Outstanding raw material and utility yields
Process advantages: • Consistent high-quality products widely accepted in the market-
• Regular and flame-retardant grades available place
Continued 
Polystyrene, expandable, continued
• Best packaging grade offer of the market and universal flame-
retardant product range
• Clean process
• High quality yields (above 99% prime)
• High selectivity allowing to fit market demand
• High reliability Organic suspension technology Mineral suspension technology
• Ongoing development of new and improved, market-specific
formulations
• Excellent technical support from INEOS.
Commercial plants: The technology has been selected three times with
the award of a 40,000 metric tpy capacity plant in 1997; a 50,000 met-
ric tpy plant in 2004; and 50,000 metric tpy facility in 2007.

Polystyrene, general purpose (GPPS)

Application: To produce a wide range of general purpose polystyrene
(GPPS) with excellent high clarity and suitable properties to process PS Styrene
foam via direct injection extrusion by the continuous bulk polymeriza- Solvent 2
Additives
tion process using Toyo Engineering Corp. (TOYO)/Mitsui Chemicals Inc. 1 Preheaters
technology.
Reactor
3 Devolatilizers
Description: Styrene monomer, small amount of solvent and additives
are fed to a specially designed reactor (1) where the polymerization is Condensers
Vacuum
carried out. The polymerization temperature of the reactor is carefully
4
controlled at a constant level to maintain the desired conversion rate. Recovered monomer
The heat of polymerization is easily removed by a specially designed
Storage Pelletizer Die head
heat-transfer system. 6 5
At the exit of the reactor, the polymerization is essentially complete.
The mixture is then preheated (2) and transferred to the devolatilizers
(3) where volatile components are separated from the polymer solution
by evaporation under vacuum. The residuals are condensed (4) and re-
cycled back to the process. The molten polymer is pumped through a
die (5) and cut into pellets by a pelletizer (6).
Economics: Basis: 50,000 metric tpy GPPS

Raw materials consumption per metric ton of GPPS, kg 1,009
Utilities consumption per metric ton of GPPS,US$ 10.5
Commercial plants: Six plants in Japan, Korea, China, India and Russia
are in operation, with a total capacity of 200,000 metric tpy.
Licensor: Toyo Engineering Corp. (TOYO)/Mitsui Chemicals Inc.

- CONTACT

Polystyrene, high-impact (HIPS) Styrene

Application: To produce a wide range of high-impact polystyrene (HIPS) Rubber
Solvent
with well-balanced mechanical properties and processability via the
Additives
continuous bulk polymerization process using Toyo Engineering Corp. Prepolymerizer
(TOYO)/Mitsui Chemicals Inc. technology. The process provides a swing
production feature and is also capable of producing general purpose 5
Reactors
polystyrene (GPPS). 1 3 4 Preheaters
Description: Styrene monomer, ground rubber chips and small amount 2 6 Devolatilizers
of additives are fed to the rubber dissolver (1). The rubber chips are
completely dissolved in the styrene. This rubber solution is sent to a Dissolver Feed tank Condensers
Vacuum
rubber-solution-feed tank (2). The rubber solution from the tank is sent
7
to the prepolymerizer (3) where it is prepolymerized, and the rubber Recovered monomer
morphology is established.
Storage Pelletizer Die head
The prepolymerized solution is then polymerized in specially de- 9 8
signed reactors (4) arranged in series. The polymerization temperature
of the reactors is carefully controlled at a constant level to maintain
the desired conversion rate. The heat of the polymerization is easily re-
moved by a specially designed heat-transfer system.
The polymerization product, a highly viscous solution, is preheated
Commercial plants: Six plants in Japan, Korea, China and India are in
(5) and transferred to the devolatilizers (6). Volatile components are sep-
operation, with a total capacity of 190,000 metric tpy.
arated from the polymer solution by evaporation under vacuum. The
residuals are condensed (7) and recycled to the process. The molten Licensor: Toyo Engineering Corp. (TOYO)/Mitsui Chemicals Inc.
polymer is pumped through a die (8) and cut into pellets by a pelletizer - CONTACT
(9).
Economics: Basis: 50,000-metric tpy HIPS unit

Raw materials consumption per metric ton of HIPS, kg 1,009
Utilities consumption per metric ton of HIPS, US$ 8

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Petrochemical Processes 2010 Home Process Categories Company Index

Normal paraffins, C10 – C13

Feedstock is typically straight-run kerosine with 18 – 50% normal

Commercial plants: Thirty-two Molex units have been built.

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Yields: Nearly 80% conversion of n-butenes can be attained and se-

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Olefins—butenes extractive distillation

Description: In the extractive distillation (ED) process, a single-com- C4 olefins

Commercial plants: Two commercial plants for the recovery of n - butenes

Licensor: Uhde GmbH - CONTACT

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Product: Propylene (polymer- or chemical-grade); isobutylene; n-buty- Hydrocarbon feed

Copyright © 2010 Gulf Publishing Company. All rights reserved.

References: Heinritz-Adrian, M., N. Thiagarajan, S. Wenzel and H. Gehrke,

Licensor: Uhde GmbH - CONTACT

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Description: The DCC process selectively cracks a wide variety of feed-

Commercial plants: At present, eight units are in operation: six in China,

Reference: Dharra, et al., “Increase Light Olefins Production,” Hydro-

Licensor: The Shaw Group - CONTACT

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Commercial plants: There are four MSTDP units (predecessor technology

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Commercial plants: There are three MSTDP units (predecessor technol-

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Investment, US$ million 363

Commercial plants: UOP is the world’s leading licensor of process tech-

Licensor: UOP LLC, A Honeywell Company - CONTACT

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Description: Fresh feed containing an equilibrium mixture of C8 aro- 3 4 5 6

equilibrium mixture of C8 aromatic isomers. Hydrogen-rich recycle gas

Paraxylene Light ends

Description: The PX-Plus XP Process is composed of three processing

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Paraxylene, crystallization Primary

for production of paraxylene (PX). The process can be applied in a sin-

arrangement of equipment to obtain the required recovery and product

Commercial plants: Three commercial licenses.

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Petroleum coke, naphtha,

Application: The delayed coking technology is a thermal-cracking

Description: Key points for the delayed coking technology include:

Commercial plants: SINOPEC has independently designed and erected

Licensor: China Petrochemical Technology Co., Ltd. - CONTACT

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Polyalkylene terephthalates— ESPREE

Description: Based on the innovative and patented design modifications Resin

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Application: Process to produce polyesters from the polyalkylene

Description: A slurry composed of a dicarboxylic acid and a diol is pre-

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Copyright © 2010 Gulf Publishing Company. All rights reserved.

Polyethylene Diluent recycle

Licensor: Borealis A/S - CONTACT

Copyright © 2010 Gulf Publishing Company. All rights reserved.