Chapter 2: Aromatics

Feed to the Platforming unit is mixed with recycled hydrogen gas,

preheated by a feed effluent exchanger, further heated to reaction
temperature by a fired heater, and then charged to the reactor
section.
Because most of the reactions that occur in the Platforming process
are endothermic, the reactor section is separated into several
stages, or reactors. Fired heaters are installed between these
reactors to reheat the process stream up to the correct
temperature for the next stage.
Effluent from the last reactor is cooled by exchanging heat with the
feed for maximum heat recovery.
Additional cooling to near-ambient temperature is provided by air
or water cooling.
The effluent is then charged to the separation section, where the
liquid and gas products are separated.
A portion of the gas from the separator is compressed and recycled
to the reactor section.
The net hydrogen produced is sent to hydrogen users in the
refinery complex or to the fuel header.
The separator liquid is pumped to a product stabilizer, where the
more-volatile light hydrocarbons are fractionated from the high-
octane liquid product.
The first Platforming units were designed as semiregenerative (SR), or fixed-bed, units employing monometallic catalysts.
Semiregenerative Platforming units are periodically shut down to regenerate the catalyst. This regeneration includes burning off
catalyst coke and reconditioning the catalyst’s active metals. To maximize the length of time (cycle) between regenerations,
these early units were operated at high pressures in the range of 2760 to 3450 kPa.
UOP initially improved the Platforming process by introducing bimetallic catalysts to SR Platforming units. These catalysts
enabled a lower-pressure, higher-severity operation: about 1380 to 2070 kPa, at 95 to 98 octane with typical cycle lengths of 1
year. The increased coking of the catalyst at the higher severity limited the operating run length and the ability to further reduce
pressure. Catalyst development alone could not solve these problems; process innovations were needed. In the 1960s, cyclic
reforming was developed to sidestep this barrier. Cyclic reforming employs fixed-bed reforming, but the reactors can be
individually taken off-line, regenerated, and then put back into service without shutting down the unit and losing production.
Fixed Monometallic Moving bimetallic

bed
catalyst
bed catalyst

2760-
6-18 months 3450 3 days ?
kPa
3-4 years
kPa

490- ON:
525- ON: +12
hydrogenx2,
525 oC 540 oC hgghẻ C5
yield
The ability to continuously regenerate a controlled quantity of
catalyst is the most significant innovation of the CCR
Platforming unit. The catalyst flows by gravity from the last
reactor into an integral (to the reactor) catalyst collector vessel.
The catalyst is then lifted by either nitrogen or hydrogen lifting
gas to a catalyst hopper above the regeneration tow- er. Catalyst
flows to the regeneration tower, where the catalyst is
reconditioned. Regenerated catalyst is then returned to the top
of the reactor stack by a transfer system similar to that used in
the reactor-regenerator transfer. Thus, the reactors are
continuously supplied with freshly regenerated catalyst, and
product yields are maintained at fresh catalyst levels.
The regeneration and reactor sections of the unit are easily
isolated to permit a shut- down of the regeneration system for
normal inspection or maintenance without interrupting the
Platforming operation.
Improvements are continuously being made in the CCR
regeneration section design. In addition to its atmospheric and
pressurized regenerators, UOP introduced the CycleMax*
regenerator in 1995 which combines new innovations with the
best aspects of previous CCR designs at lower cost.
Activity stability is a measure of the rate at which the catalyst
deactivates over time. In semiregenerative reforming, stability is an
indication of how long the catalyst can remain in operation between
regenerations. In CCR Platforming, stability is an indication of how
much coke will be formed while processing a given feed at a given
severity, which, in turn, determines the size of the catalyst
regeneration section.
Since the catalyst is not regenerated in situ, the
reactor section operates only in its pri- mary
function of providing the catalytic environment
for the reforming reactions. It is therefore not
exposed to harsh regeneration conditions and is
less prone to corrosion and fouling than SR
Platforming.
Pressure?
Decreasing the reactor pressure increases
hydrogen and reformate yields, decreas-
es the required temperature to achieve
product quality, and shortens the catalyst
cycle because it increases the catalyst
coking rate. The high coking rates
associated with lower operating
pressures require continuous catalyst
regeneration.
Benefits CCR Platforming technology has been the industry leader
in reforming technology since the first unit came on stream in 1971
for many reasons. High utilization of feed due to low operating
pressure.
• High on stream factor of more than 98%
• Flexibility to process a wide variety of feedstock.
• Minimal catalyst attrition.
• Stacked reactors for economical design.
• Optimized heat and compression integration for every unit.
• Liquid recovery optimized on every unit
 Aromatics Complex
Petrochemical Markets

120

100
LAB
80 Acetic Acid
World PX
Demand, 60 MeOH
MM MTA Benzene
40 Propylene
Ethylene
20

0
Petrochemical Landscape: Aromatics
Kerosene Naphtha Gas Oil Propane Natural Gas

Steam
Reforming
Catalytic
Reforming Aromatics Methanol
Complex
Steam
PAREX Isomar Tatoray Cracking Oleflex MTO

Benzene (T, o-X, m-X) p-Xylene Ethylene Propylene

Molex Ethyl- Cumene PTA EO/EG PE PP Vinyl Acetate

benzene

Pacol Styrene Phenol PET (SSP)

Detal PS Capro
/Nylon

LAB Polystyrene Polycarbonate Polyethylene Acrylics

Detergents Nylon Polyester Polypropylene
Key
Process, Catalyst/Adsorbent, Equipment & Services
Process Technology and Services
Catalyst/Adsorbent, Equipment & Services
Alliance
Aromatics Markets
30
Other BZ BZ to Cyclohexane
25 BZ to Phenolics BZ to Styrenics
over 1999 - MM MT p-Xylene
20 6.8%
Demand Increase

15

10
3.6%
5

0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Strong Aromatics & Derivatives Growth

Sources: CMAI & UOP
Aromatics Complex Flowsheet
Units in the aromatics complex
Process Unit Licensed Operating
CCR Platforming 258 208
Sulfolane 150 129
Tatoray 51 42
Parex 91 76
Isomar 72 58
Benzene Recovery: Sulfolane
Sulfolane Process
Extraction of aromatics from non-aromatics
SULFOLANE Sulfolane is the preferred solvent for
this process due to its high selectivity
for the aromatics of interest and its
capacity for dissolving large quantities
of aromatics in relatively low quantities
of solvent. For its selectivity, capacity,
and low boiling temperature, the
sulfolane extraction process is less
expensive to operate than similar
processes using other solvents.
Following extraction, more non-aromatics are removed from the sulfolane and
aromatic stream using extractive distillation. After extractive distillation, the
aromatics must be separated from the sulfolane using an aromatics recovery
column. This column separates the components by employing the large difference in
boiling temperature. Sulfolane has a very low boiling temperature (545°F) relative to
other solvents, which makes it especially valuable in the recovery process. In a well-
maintained system, the separated aromatics are of high purity (> 99% by weight)
and most of the aromatics are recovered (> 99%). At a sulfolane loss of
approximately 5-10 ppm of feed for a 10,000 BPD feed plant, about 10,500 pounds
of solvent is lost per year, resulting in a sulfolane recovery rate greater than 99%
(TTC).
 Extractive
Processes
for BTX
Recovery

The characteristics that are most important in an

extractive solvent are the solvency and the
selectivity for compounds of interest. In the case of
oil refining, the compounds of interest are
benzene, toluene, and xylenes (BTX). However,
other characteristics must be taken into account
such as the chemical stability, compatibility,
availability, price, and environmental hazards. The
efficiency of sulfolane is difficult t
THDA: ?
Tatoray Process

toluene
C9 aromatics

zeolite
 Main demand is for pX to make polyester resin

 Demand for toluene as product is minimal.

 Toluene and C9 aromatics are only worth gasoline

C8 aromatics
blending value (high octane)

New TA-30 Catalyst  Transalkylation shifts methyl group to increase yield of

based on UZM-14
P-Xylene Recovery: Parex
 Separating the C8 Isomers
• C8 aromatics boil too close to separate by distillation.

Mixture Relative Volatility Number of

Stages*
MX/OX 1.147 150

EB/PX 1.058 350

PX/MX 1.019 800

• Phillips developed fractional crystallization in 1962.

• Esso first demonstrated chromatography using molecular sieves in 1964, but productivity
was too low.

* To 99% pure products

Counter current adsorption was developed for p-Xylene separation

 Clarence Gerhold and Don Broughton’s

SORBEX SMB process switched net flows
through a sequence of packed beds to simulate
solid flow.

 Originally invented for separating paraffin

isomers to raise gasoline octane number and
first commercialized as MOLEX.

 Allowed continuous adsorption using mol sieves

that couldn’t withstand flowing.

 PAREX application to xylene separation

commercialized in 1971.
1917 - 1984
SORBEX™ Process
P-Xylene separation by SORBEX Technology
PAREX Unit

 93 units now
licensed

 Largest single train

designed for 1
MMTA

 Total capacity over

18 million MTA of
PX
para-Xylene Production Technologies

UOP Parex accounts for ~ 68% of world p-X production

Increasing p-X yields: Isomar
Isomar Process
 Main demand is for pX to make
Metal
+ H2 polyester resin
EB
 EB, mX oX and pX can be brought
mX
back to equilibrium over a suitable
oX catalyst
Acid
 EB is harder to isomerize so two
types of Isomar
 EB dealkylation (to Bz)
Metal  EB isom (to C8 mix)

+ paraffins due to cracking

pX

~24 mol% pX eqbm yield

Isomar Flowscheme

Reactor Light Ends

Net Gas

Product Net
Separator Liquid
Charge
Heater
Deheptanizer

Combined Feed
Exchanger Clay
Treater
Product
Condenser
To Aromatic
Compressor Fractionation Unit

Feed from Makeup H2

Parex Unit
Ethylbenzene
and
Styrene
1. Alkylation of Benzene
• Benzene + ethylene to Ethyl benzene
• Catalyst: AlCl3 granules
• C2H5Cl provides hydrogen and
chlorine free radicals
• Operating conditions: 95oC and 1 atm
pressure
• Reaction is exothermic

2. Dehydrogenation of ethylbenzene
• Ethylbenzene to Styrene + Hydrogen
• Reaction is endothermic
• Catalyst: SnO or FeO
• Operating conditions: 800oC
- Benzene (wet) is sent first to an azeotropic distillation unit that separates water and produces dry
Benzene.
-  Dry Benzene + Ethylene + Ethyl chloride + AlCl3 enter the alkylator catalyst
-  The reactor could be a jacketed tower where water is used as a cooling fluid in
the jacket to control the reactor temperature.
-  The reactor produces two products namely uncondensible gases and the liquid product in which AlCl3
complex is available. This complex needs to be regenerated and sent back to the alkylator.
-  The alkylator product is sent to a cooler which upon cooling to 40oC separates the aluminium chloride
complex stream from the product stream. The other stream from the cooler is the ethylbenzene rich
product stream.
-  The aluminium chloride stream is partially recycled to the alkylator so as to maintain the required
catalyst requirements. The other portion of the AlCl3 complex is sent to a dealkylator unit in which the
feed is heated to 200 oC. By doing so, the polyethylbenzenes formed in the alkylator are converted to
benzene and ethylbenzene (cracking reaction).
-  The benzene and ethylbenzene are returned to the cooler.
-  The delkylator produces a residue product consisting of tar + AlCl3 mixture.
-  The product stream from the cooler consisting of ethylbenzene is mixed with 50 % NaOH to remove
acidic impurities. Eventually, after settling waste is eliminated.
-  The purified ethylbenzene then enters a stripper that separates ethylbenzene +
benzene from the polyalkylbenzenes. The polyalkylbenzenes are sent to a polyalkyl still that separates the
benzene + ethylbenzenes from the polyalkylbenzenes (bottom product). The polyalkyl still is operated
under vacuum. The polyalkylbenzenes are fed to the dealkylator and the benzene + ethylbenzene rich
stream is sent to a heat integrated exchanger that extracts heat from the vent gases and then eventually
enters the alkylation reactor.
-  The top product from the stripper is ethylbenzene + benzene and it enters a benzene column that
separates wet benzene from crude ethylbenzene. The wet benzene is recycled to the azeotropic dryer
where it is mixed with fresh wet benzene to enter the azeotropic dryer.
-  The crude ethylbenzene is further purified in a fractionator where the bottom product (with benzene) is
mixed with the top product of the polyalkyl still. Thereby, the stream enters the heat integrated exchanger.
-  The ethylbenzene is further subjected to caustic wash and finally it is sent to a dryer to produce dry
ethylbenzene.
• Wet benzene được đưa
đến thiết bị chưng cất
azeotropic để tách nước
để tạo “dry benzene”.

• “Dry benzene” để tránh

các phản ứng không cần
thiết trong lò phản ứng
alkyl hóa cũng như làm
hỏng chất xúc tác.
• Dry Benzene + Ethylene + Ethyl
chloride + AlCl3 enter the alkylator

• Lò phản ứng có thể là một TB vỏ áo,

nước được sử dụng làm chất làm mát
để điều khiển nhiệt độ lò phản ứng.

• Lò phản ứng tạo ra hai sản phẩm: khí

không ngưng và sản phẩm lỏng có
chứa AlCl3. Hỗn hợp này cần phải tái
sinh và quay lại thiết bị alkyl hóa.

• Sản phẩm alkyl hóa được đưa đến tb

làm mát đến 40oC sẽ tách AlCl3 khỏi
dòng sản phẩm. Dòng còn lại là dòng
giàu ethylbenzene.
• Một phần AlCl3 quay lại tb alkyl
hoá để duy trì chất xúc tác. Phần
AlCl3 còn lại đến dealkylator. Ở đó,
polyethylbenzene được chuyển
thành benzene và ethylbenzene.

• The benzene and ethylbenzene

are returned to the cooler.
• The delkylator produces a residue product
consisting of tar + AlCl3 mixture.

• From this mixture, AlCl3 is recovered using

water extraction as AlCl3 is soluble in water.
From there AlCl3 is recovered from the water
and returned back to the alkylation reactor.

• The product stream from the cooler consisting

of ethylbenzene is mixed with 50 % NaOH to
remove acidic impurities. Eventually, after
settling waste is eliminated.
• Stripper: tách EB và B ra khỏi
polyalkylbenzene
• Polyalkyl still (vacuum): tách B và EB khỏi
polyalkylbenzene
• Polyalkylbenzene được đưa đến dealkylator
• B + EB (từ polyalkyl still): đến heat
exchanger, vào alkylator
• EB + B (từ stripper): qua benzene column
• Benzene column: tách wet B ra khỏi EB
• Ethyl Benzene column: tách EB out
• Trung hoà và làm khô EB
Vai trò của C2H5Cl:

H2O: gây ăn mòn, giảm hoạt tính xt do pha loãng

Benzene: < 30 ppm H2O
Phản ứng pha lỏng
• The ethylbenzene (dry) is heated with superheated steam to enter the
catalytic dehydrogenator. Excess steam is used in this process. The feed pre-
heating is carried out using the product vapour stream. The reaction is gas
phase
catalytic reaction.
• The vapour stream after cooling with the feed stream in a heat integrated
exchanger is fed to a quench tower using steam quenching.
• After quenching, partial condensation of the quenched vapors produces three
streams one being the vapour vent, the other being water and the third being
the organic phase rich with styrene.
• The styrene rich stream is sent first to a benzene column to recover the
benzene + toluene and this is sent to a benzene-toluene distillation column to
recover benzene. The benzene is sent to the azeotropic distillation unit as a
raw-material.
• The bottom product from the benzene column enters an ethylbenzene
column which separates ethylbenzene from the styrene stream. The
ethylbenzene stream is mixed with the dry ethylbenzene to enter the catalytic
dehydrogenator.
• The bottom product from the ethylbenzene column is the styrene enriched
stream and this is sent to the finishing column where styrene is further purified
from unwanted impurities such as tar. The tar is further batch distilled to
recover styrene from the tar. The styrene finishing column also produces
styrene product. Both styrene products from batch still and styrene finishing
column are mixed and cooled to store as styrene product.
• All three columns namely benzene, ethylbenzene and finishing columns are
operated under vacuum.
Câu hỏi:
1. Wet benzene to dry benzene?
2. B + EB stream: back to cooler but not alkylator
3. Tại sao phải cho AlCl3 quay lại alkylator?
4. Tại sao PAB lại có mặt ở dòng EB?
5. Tại sao EB + B lại có ở đáy stripper?
6. Tại sao B sau benzene column lại wet?
7. Caustic wash + drying: cho EB stream?
8. Tại sao polyalkyl still: vacumn?
9. Why separation of benzene, toluene, EB and styrene: vacumn?
10.Why tar consist of styrene?
11.Khí nào ra vent ở tháp quenching?
12.Why steam quenching but not water quenching?