Chapter 2:

AROMATIC HYDROCARBON PRODUCTION

Assoc. Prof. Pham Thanh Huyen

Department of Petrochemical and Organic Synthesis
School of Chemical Engineering
[email protected]
 Content

2.1. Introduction
2.2. Sources of aromatic hydrocarbons
2.3. Application of aromatic hydrocarbons
2.1. Introduction

2.1.1. Physical proper1es

2.1.2. Aroma1cs Markets

2.1.1. Physical Properties

Properties Unit Benzene Toluene o- m-Xylene p- Mixed

Xylene Xylene xylene
Mr 78.11 92.13 106.16 106.16 106.16 106.16
Density at 20°C 0.879 0.867 0.876 0.86 0.857 0.86

mp °C 5.53 - 94.99 -25.2 -48 +13.3 -25

bp °C 80.1 110.6 144.4 139 138.4 138.5
Ignition temp. °C 498 552 465 530 530 464
Explosion limits in air Vol%
Lower 1.4 1.3 1.1 1.1 1.1 1.0
Upper 7.1 6.8 6.4
distillation6.4
??? 6.6 67.0
Flash point °C -11.1 4.4 17.2 25 25 27-32
Vapor density (air = 1) 2.77 3.14 3.7 3.7 3.7 3.7

Azeotropic distillation, Extractive

Distillation
2.1.1. Physical Properties

Benzene: 80.1

Toluene: 110.6

o-xylene: 144,4

m-xylene: 139

p-xylene: 138,4
2.1.1. Physical Properties

- Aromatics hydrocarbon are insoluble in water but

soluble in organic solvents
- Adsorbed by solid adsorbents

How to separate ???

Liquid – liquid extraction, Extractive

Distillation, adsorption
2.1.2. Aromatics Markets

30
Other BZ BZ to Cyclohexane
25 BZ to Phenolics BZ to Styrenics
over 1999 - MM MT p-Xylene
Demand Increase

20

15

10

0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Strong Aromatics & Derivatives Growth

2.1.2. Aromatics Markets

50
p-Xylene Capacity & Demand
Sources: PCI & UOP
45
Future • Refineries are main
40 supply
35 deficit source of xylenes
p-Xylene, MMTA

30 Global Demand
supply
25 Production
Capacity
20
15
• Future p-X demand
10
growth expected to
5
average 1.8M MTA/Yr
0
92

96

00

04

08

12

16
19

19

20

20

20

20

20

UOP 4698-10
2.2. Sources of aromatic hydrocarbons

2.2.1. Catalytic Reforming

2.2.2. pyrolysis gasoline
2.2.3. Production from coal
2.2.4. Hydrocarbon conversion

2.2.5. Aromatic hydrocarbon separation

 2.2.1. Catalytic Reforming
CCR Unit in refinery

Mohamed A. Fahim, Taher A. Alsahhaf and Amal Elkilani, Fundamentals of Petroleum Refining, Elsevier, 2010
2.2.1. Catalytic Reforming

- Reactions.
- Catalysts
- Operating conditions
2.2.1. Catalytic Reforming

Reforming Reactions

DH, kJ/mol >0

Ü Endothermic, volume
increase
à high temperature, Low
pressure
2.2.1. Catalytic Reforming

Reforming Reactions

- Coke formation is favoured at low partial pressures of hydrogen.

- The catalyst has to be re-activated by burning off the deposited coke
2.2.1. Catalytic Reforming
2.2.1. Catalytic Reforming

- Catalysts: bifunctional catalyst of Pt/g-Al2O3

+ acidic function (g-Al2O3): promote the isomerization and

cyclization

+ Metal function (Pt): promote the dehydrogenation,

hydrogenation

- Promoter: Re, Ir, Ru, Ag, Au, Ge... RCl

2.2.1. Catalytic Reforming

Role of Reformer in the Refinery

• Gasoline (37 wt% of the total gasoline pool).

• Aromatics
???
• H2
– recycled to the naphtha hydrotreater,

– sent to other units demanding hydrogen

2.2.1. Catalytic Reforming
2.2.1. Catalytic Reforming
Reformer cuts and reformate composition (amounts in wt %)

Research octane number: indicates relative degree of reforming severity

2.2.1. Catalytic Reforming

Feedstocks – Products
700C 1050C 1450C

BT Catalytic Reforming

Xylene Catalytic Reforming

BTX Catalytic Reforming

I.F.P (Institut Francais du Petrole)

2.2.1. Catalytic Reforming
2.2.1. Catalytic Reforming

Radial and Axial fixed bed reactor

Exercise: Pros and cons of Radial and Axial Fixed Bed reactor
2.2.1. Catalytic Reforming
2.2.1. Catalytic Reforming

The spent catalyst is regenerated in four steps:

• Burning of the accumulated coke

• Oxychlorination – for dispersing the catalyst metals and adjusting

the catalyst chloride content

• Catalyst drying

• Reduction – for changing the catalyst metals to the reduced state

2.2.1. Catalytic Reforming
Simplified AXENS’ Aromizing Flowscheme
2.2.1. Catalytic Reforming
2.2.1. Catalytic Reforming
2.2.1. Catalytic Reforming

CCR- BSR
2.2.2. Pyrolysis gasoline Typical composition of naphtha pyrolysis gasoline

Components fraction (%)

Suitable
C5+
gasoline
for
C6-200°C
gasoline?
fraction
C6-C8
fraction
Parafin and naphthen 11.8 7.8 9.7
Olefin 5.5 2.4 3.0
Diolefin Gum formation
Ü 18.1 8.7 5.9
Aromatic hydrocarbon
Benzene Üinfluent
28.0 the solvents
35.2 43.7 used
Toluene 13.9 17.4 21.7
C8 7.2 9.0 11.3
Aromatic alkene (Styren) èhydro
3.0 treating
3.8 4.7
C9+ 12.5 15.7 -
- hydrodedien è selective hydrogenation of diolefin
Total aromatic hydrocarbons 64.6 81.1 81.4
- hydrodesulfurization è S removal
Total 100.0 100.0 100.0
Sulfur content (ppm) 220 180 150
2.2.2. Pyrolysis gasoline
2.2.3. Production from coal

- Light oils from the carbonization or coking of coal

- In the coking of coal, the yields and composition of the light oils depend on the
type of coal being processed and on the carbonization temperature.
- Typical composition of light oils produced in coke-oven operation is (vol%):
- benzene 63
- toluene 13
- xylenes 8
- higher aromatics 10
- Nonaromatics 6

Coal à BTX, naphtalene, antracene, phenantren... RH

Practice Quiz 4
 Bài tập: Phân biệt các quá trình sau

Cracking hơi nước Cracking xúc tác

Reforming hơi nước Reforming xúc tác

 Bài tập: Phân biệt các quá trình sau

Hydrodealkyl hoá Isome hoá

Bất phân bố toluen Cyclar

2.2.4. Hydrocarbon conversion
2.2.4. Hydrocarbon conversion

(Methods of Increasing Production)

2.2.4.1. Hydrodealkylation
2.2.4.2. Isomerization
2.2.4.3. Toluene disproportionation
2.2.4.4. Cyclar process
2.2.4. Hydrocarbon conversion

2.2.4.1. Hydrodealkylation
- Purpose: increase benzene production from other aromatic compounds
depending on demand
- Reactions CH3

CH3
+ H2 + CH4
+ H2 +CH4

- Side products
+ biphenyl formation
2

+ benzene hydrogenation biphenyl

+ carbon formation.
2.2.4. Hydrocarbon conversion

- Processes

+ Thermal Hydrodealkylation

Ü Atlantic Richfield and Hydrocarbon Research Inc,

Mitsubishi and Chioda, Gulf Oil, UOP

+ Catalytic hydrodealkylation: 10-15% Cr2O3/Al2O3

ÜShell, UOP, Houdry and BASF

àDetol Process, Hydeal Process (Ashland Oil and UOP),

HDA Process, THD Process (Gulf process), MHC
Process (Mitsubishi Petrochemical Co.)
2.2.4. Hydrocarbon conversion

- Hydrodealkylation reaction conditions

Thermal Catalytic
Inlet temp. 620°C, 620°C,
Maximum temp. 730-750°C 700-720°C
Pressure 4.3 Mpa 4.5 Mpa
Molar ratio of H2: hydrocarbon 4 6
Conversion, % 75 70

Yield 97-99% mol 97% mol

Catalyst lifetime - 2 years

è Regeneration by coke burning
2.2.4. Hydrocarbon conversion

1. Despite removing H2 and

CH4 from the phase
separator, why again we
remove them from the gas
stripper unit ?
2. Comment upon fuel
efficiency in the process
and possibilities to
enhance it ?
3. Do you suggest to put one
more distillation column
for the heavy end
compounds. If so why ?
2.2.4. Hydrocarbon conversion

2.2.4.2. xylene isomerization

- Purpose: to maximize the yield of o- and p-xylenes by using
catalytic conversion processes.

C2H5 CH3 CH3 CH3

CH3

CH3
CH3
o-xylene m-xylene p-xylene

??? EB source? Why isn’t EB obtained from catalytic reforming?

2.2.4. Hydrocarbon conversion

- Acid catalysts.
+ Conventional catalysts:
Friedel Craft AlCl3 + HCl
HF+BF3 complex
® Liquid phase at 500C
+ solid catalysts:
Aluminosilicate or zeolite X, Y
The acidic metal-containing zeolite Pt/H-ZSM-5, Pt/H-Mordenite (Mobil)
Pt/Al2O3, Pt/SiO2-Al2O3
® Gas phase at 400-5000C
2.2.4. Hydrocarbon conversion

- Gas phase isomerization process

SiO2-Al2O3, Al2O3 Pt/SiO2-Al2O3 or Pt/Al2O3

Temp. 400-500°C, 300-500°C,
Pressure 0,1-2 Mpa 1-3 Mpa
H2: RH mole ratio 0 8-10
Reactor type adiabatic fixed bed

Coke formation

è1 reactor + 1 regenerator
2.2.4. Hydrocarbon conversion
UOP xylene isomerization
CH3 CH3 CH3
CH3

CH3
CH3
2.2.4. Hydrocarbon conversion

2.2.4.3. Toluene disproportionation or transalkylation

ØProcesses have been developed to disproportionate or transalkylate alkylated
aromatics to produce benzene and alkylated benzenes.
2Toluene ® benzene + xylene
Toluene + trimethyl benzene ® 2xylene
ØReactions:
2.2.4. Hydrocarbon conversion
2.2.4. Hydrocarbon conversion

Reaction temp. 350 – 525 °C

Pressure 1 – 5 Mpa
Catalysts:
- H-Mordenit (Mobil)
- ZSM-5 (UOP/Toray)

( Ullmann’s)

- Re/g-Al2O3 (Nghi Sơn)

2.2.4. Hydrocarbon conversion

T.-C. Tsai et al. / Applied Catalysis A: General 181 (1999) 355-398

2.2.4. Hydrocarbon conversion
Temp, degC
Press, MPAg
482
- Off gas TATORAY (Transalkylation)
Flow, kg/Hr 292,297 to F/G
NNF
463 Reactor
55 - #1 Reactor
40 292,297
902

M/U H2
499
57 Heater - Transalkylation
40 292,297
85888 Activity
178
-
46
-
M
206,409 207312 Recycle gas
139 compressor
Toluene -
To Stripper
C9A+ 292,297

CH3 CH3
Reaction Cat Reactors design
2 + - ID ; 4,800mm
CH3 - H(TL-TL) ; 3,500 mm
Transalkylation CH3 CH3 CH3
reaction of Main Catalyst information
Toluene & C9+A + Cat 2 - Carrier ; Al2O3
- Activated Metal ; Rhenium
(CH3) 2 CH3
2.2.4. Hydrocarbon conversion
2.2.4. Hydrocarbon conversion
2.2.4. Hydrocarbon conversion

2.2.4.4. Cyclar Process

Purpose: LPG ® Ar
Reactions:
+ Dehydrogenation C3, C4 ® C3=, C4=
+ Oligomerization ® C6=, C7=, C8=
+ Dehydrocyclization C6=, C7=, C8= ® Ar
Eg. CH3-CH2-CH3 ® CH3-CH=CH2 + H2
2CH3-CH=CH2 ® CH3-CH2-CH2-CH2-CH=CH2

CH3CH2CH2CH2CH=CH2 + 3 H2

Liquid product composition

+ 92 wt.% BTX
+ 7-8 wt.% aromatic hydrocarbon C9 and C10
2.2.4. Hydrocarbon conversion

2.2.4.4. Cyclar Process

DHå >0
2.2.4. Hydrocarbon conversion

2.2.4.4. Cyclar Process

Similar to UOP CCR Platforming

vReaction temp. 535oC
vPressure :6 bar
vResidence time:14s
vCatalyst Zn or Ga/ZSM-5
2.2.5. Aromatic hydrocarbon separation
AXENS’ Typical Aromatics Complex
Morphylane extractive distillation unit
Sulfolane liquid-liquid extraction process.

EB-reforming
Adsorption
technology (Oparis)
EB dealkylating technology (XyMax)
2.2.5. Aromatic hydrocarbon separation

Axens’ ParamaX packages:

• Aromizing - high severity CCR reforming for aromatics production,
• Arofining - reformate olefins saturation (hydrogenates undesirable olefins and diolefins present in the
high severity reformate).
• Sulfolane (Lyondell) - high purity benzene, toluene and xylenes extraction,
• Morphylane (Uhde) - toluene and high purity benzene extraction,
• Eluxyl - simulated countercurrent adsorption PX separation,
• Crystallization - production of ultra-high purity PX when combined with Eluxyl in the hybrid version,
• Oparis - new generation xylenes and ethylbenzene (EB) isomerization,
• XyMaxSM (ExxonMobil) - xylenes isomerization with EB dealkylation, using the newly commercialized
EM-4500 catalyst with improved activity and selectivity,
• PxMaxSM (ExxonMobil) - state-of-the-art Selective Toluene DisProportionation (STDP) technology for
the production of a highly PX-enriched xylene stream and benzene,
• TransPlusSM (ExxonMobil) - toluene/C9+C10 aromatics transalkylation, with the proven ability to
process high amounts of C9 and C10 aromatics,
• MTDP-3 (ExxonMobil) - toluene disproportionation to benzene and xylenes.
2.2.5. Aromatic hydrocarbon separation
2.2.5. Aromatic hydrocarbon separation
C5~C7 Non Aromatics Recycle Mogas Pool
Benzene
Off
Gas
NSRP DLN
Aromatics
Extraction
C6/C7
Distillation
Toluene

(C5) TA
ISOMER C9/C10
Aromatics NHDS C6~C9 Aromatics
Mogas Pool
complex DHN
LPG C7-
(C6~C9+)
CCR C8+
FRN C7- PX PX
Reformate
Reformate Recovery
Splitter Xylenes H2
C8+ EB

CDU Xylene Xylene

Splitter Isomer Off Gas
(Deheptanizer)
C9+
HAC Mogas Pool
C10+ Fuel Oil
2.2.5. Aromatic hydrocarbon separation
Integration of xylene production into petrochemical refineries
2.2.5. Aromatic hydrocarbon separation

Benzene: 80.1

Toluene: 110.6

O-xylene: 144,4

M-xylene: 139

P-xylene: 138,4

EB: 136.2
2.2.5. Aromatic hydrocarbon separation

crystallization
Complexation

O-xylen (min 98%)

Yield >95%
adsortion
120 – 150 trays
êT=5oC
Reflux ratio 1:10 – 1:15
Fractional distillation
2.2.5. Aromatic hydrocarbon separation

Separation of C8 aromatics
Crystallization (Chevron-Amoco)
high cost of equipment, high energy consumption
p-xylene
Adsorption : Parex (UOP), Aromax (Toray), Eluxyl
(IFP)

m-xylene Complexation with HF/BF3 Mitsubishi

o-xylene Fractional distillation

2.2.5. Aromatic hydrocarbon separation

2.2.5.1. Crystallization

2.2.5.2. Adsorption

2.2.5.3. Azeotropic distillation

2.2.5.4. Extractive Distillation

2.2.5.5. Liquid – liquid extraction

2.2.5. Aromatic hydrocarbon separation
2.2.5. Aromatic hydrocarbon separation

Melting behavior of the C8 aromatics in their mixtures

2.2.5. Aromatic hydrocarbon separation

2.2.5.1. Crystallization o- & m-xylene Ehtylene

Naphtha xylene
CCR Dryer Exchanger Exchanger Storage
(1) (2) (3) (4) vessel
(5)
Etylen l¹nh
Benzene Toluene
Propane

Storage Melting
vessel Exchanger Exchanger tank centrifuge
(10) (9) (8) (7) (6)

Propane
Melting
centrifuge tank p-xylen
(11) (12)

recycle
2.2.5. Aromatic hydrocarbon separation
p-Xylene crystallization by direct contact refrigeration

a) Drying;
b) Crystallization;
c) Centrifuge;
d) Melting tank;
e) Desorber;
f ) Scraped-surface
crystallizer;
g) Mixing tank
2.2.5. Aromatic hydrocarbon separation

2.2.5.2. Adsorption

(UOP Parex process)

Ü to separate p-Xylene (99.5%) from C8 cuts by adsorption.

• adsorbent : X ( Sr2+ ,Ba2+), Y (Na+, K+), ZSM-5

• 120 - 180°C ; 20 bar

• Desorbent : toluene, ethylbenzen or p-diethylbenzene

(low adsorption capacity)
2.2.5. Aromatic hydrocarbon separation
2.2.5. Aromatic hydrocarbon separation

A+D

B+D
2.2.5. Aromatic hydrocarbon separation

J.P. Wauquier, Petroleum Refining: Separation Processes, Edition Technip 2000

2.2.5. Aromatic hydrocarbon separation
Adsorption Separation Extract Column Finishing Column
Adsorbent Adsorbent 146 117
Chamber Chamber - -
258,376 85,777
66
-
156 571
-
298,951 Toluene to
BT Frac.

208
- 50
202,914 0.4
149 95,441
-
693,147

Raffinate 163 Paraxylene

- to Tank
Column 95,441
Xylens from Paraxylene Spec.
Xy Frac. 156 - purity ; >99.7wt%
156 - 152
- 657,081 -
424,551
328,540

156
-
Raffinate
574,916 (o-, m- Xylene)
to Isomer Temp, degC
215 Press, MPAg
-
Desobent (Paraethyl Benzene) 392,039
Flow, kg/Hr
2.2.5. Aromatic hydrocarbon separation

Typical Parex– Isomar Loop

2.2.5. Aromatic hydrocarbon separation

2.2.5.3. Azeotropic distillation

- Based on the formation of azeotropic mixtures of Ar with an azeotrope

forming agent

- Application with benzene and toluene

+ benzene: acetone is used

+ Toluene: Methanol is effective as an azeotrope forming agent in the
treatment of the toluene – xylene fractions.
2.2.5. Aromatic hydrocarbon separation

2.2.5.4. Extractive distilation.

- Extraction and extractive distillation are commonly used to separate
aromatics from crude BTX feeds.
- The solvents
+ a high-boiling polar liquid
Ü to avoid the formation of 2 liquid phases
Ü to separate from the aromatics
+ Extract Ar à non-aromatic raffinates leaves at the top of the tower
- Solvent / BTX feed ratios = 2/1 – 6/1 (according to the nature of the
solvent, column efficiency, and properties of the feedstock).
2.2.5. Aromatic hydrocarbon separation

2.2.5.4. Extractive distilation. Solvents

Company Process Solvent

Name Formular
Shell - Anilin, Fufural, nitrobenzen, phenol
(before), sulfolan (now)
O
Lurgi Distapex N-metylpyrolidone
N

O
Koppers Morphylane N-formylmorpholin
N O
SNAM Formex
Union Carbide Tetra tetraetylenglycol HO-(CH2-CH2-O)4-
H
IFP - dimetylformamide (DMF) H-CO-N(CH3)2
Toray Stex dimetyl acetamide CH3-CO-N(CH3)2
2.2.5. Aromatic hydrocarbon separation

Lurgi Distapex processs using N-metylpyrolidon as solvent

2.2.5. Aromatic hydrocarbon separation

2.2.5.5. Liquid – liquid extraction

- Extraction of aromatics from nonaromatic material by the use of a

polar solvent having a high-selective affinity for the former compounds.

- Feedstocks: Reformate, straight-run gasoline or kerosene.

- Products: Aromatic hydrocarbons for petrochemical processes, non-

aromatic solvents
2.2.5. Aromatic hydrocarbon separation

Extraction Process
2.2.5. Aromatic hydrocarbon separation

Company Process Solvent

Name Formular
Shell Sulfolan sulfolan (tetrahydrothiophen
UOP dioxide) O S

ARCO 0-5% wt of water O

O
Lurgi Arosolvan N-methyl pyrolidone + water or
etylen glycol (40% wt.) N

Union Carbide Tetra Tetraethylene glycol HO-(CH2-CH2-O)4-H

Koppers Aromex N-formylmorpholin O

N O
SNAM Formex
IFP IFP Dimethyl Sulfoxide CH3-SO-CH3
Howe Baker Aromex Diglycol amine + 7% wt. Water NH2-CH2-CH2-O-CH2-
CH2-OH
2.2.5. Aromatic hydrocarbon separation

water
+ solvent

40-150°C

Tbottom= 150-200°C

Water scrubbing
L-L Parafin
Light extraction Sovent recovery
Solvent recovery

Aromatic hydrocarbon
2.2.5. Aromatic hydrocarbon separation
 Content

2.1. Introduction
2.2. Sources of aromatic hydrocarbons
2.3. Application of aromatic hydrocarbons
2.3. Application of aromatic hydrocarbons

Handbook of Petroleum Refining Processes

2.2.5. Aromatic hydrocarbon separation

Handbook of Petroleum Refining Processes

Practice Quiz 5
Bài tập

• Từ nguyên liệu đầu là phân đoạn naphtha hoặc khí tự nhiên, hãy lựa
chọn các công nghệ thích hợp để sản xuất PS
– vẽ sơ đồ khối,
– phương trình phản ứng,
– điều kiện công nghệ…
• làm tương tự đối với PET, DEHP, PVC, PVA, Metyl axetat, ABS, MTBE