BTX aromatics (benzene, toluene, xylene)

production

Production of important organic bulk

chemicals in 2000/2001 (mio
(mio.. t/a)

Ch i l
Chemical

W ld id
Worldwide

Western
Europe

G
Germany

Ethylene

88,4

19,6

4,9

Propylene

45,9

13,4

3,5

Butadiene

7,8

2,5

0,7

Benzene

29,3

7,8

2,3

Toluene

13

2,1

0,4

Xylene

24

2,3

0,5

Applications of benzene
+ ethylene

+ H2

+ propylene

+ HNO3
benzene

+ RCH=CH2

ethyl benzene

styrene

PS, ASB, SBR

Perlon

Caprolactam
cyclohexane

cumene

nitrobenzene

alkylbenzenes

Nylon 6,6

adipic acid
Phenol

resins

acetone
Isocyanates,

aniline

paints

alkylbenzene sulfonates
(tensides)

+ O2

Maleic
anhydride

polymer
polycondensate
pesticide,

+ Cl2

chlorobenzene

paints,
pharmaceuticals

Applications of toluene
Hydeal

benzene

solvent
l
t

+ 2 HNO3

toluene

+ 3 HNO3

+ O2

+ O2

paints lacquers
paints,

dinitrotoluene

polyurethanes

trinitrotoluene

explosives

phenol

resins

benzaldehyde
fine chemicals

+ Cl2

benzyl chloride
benzodichloride
Benzotrichloride

Applications of xylene

Applications of xylene

Main sources of benzene, toluene and xylene

Gasoline from naphtha catalytic reforming unit (80%)
Pyrolysis gasoline from thermal steam cracking
byproducts in coal carbonization

Flow diagram of naphtha steam cracking

cracking gases

D
waste gas
steam
naphtha

water

steam cracker

High
pressure
steam

Cracking
(pyrolysis)
gasoline

quenching
oil

CCR platforming process for naphtha reforming

CH3

CH3

[Pt]
- H2

CH3

[Pt/Al2O3 * SiO2]

H3C

[Pt]
- H2

Composition of reformate and pyrolysis gasoline

Product

Reformate
gasoline
(wt. %)

Pyrolysis
gasoline
(wt. %)

Benzene

40

Toluene

13

20

Xylene

18

4-5

Eth l benzene
Ethyl
ben ene

23
2-3

Higher
aromatics

16

Non-aromatics

45

28-31

Coal carbonization
Product

wt. %

Coke

79

Tar

Raw benzene

Coke gas

13

Ammonia

Raw benzene

wt %
wt.

Benzene

65

Toluene

18

C8 aromatics

0,2

Higher aromatics

Sulfur

0,1

Non aromatics

Water

Currently coal carbonization does not play a role in producing aromatic bulk
chemicals.

Processes for separation and purification of BTX

Benzene is produced from pyrolysis and reformate gasoline

Toluene and Xylene are produced mainly from reformate gasoline
The products received from reforming and steam cracking are
mixtures of BTX, higher aromatics and non aromatics
For further purification and use the aromatics need to be isolated
from the non aromatics

UOP aromatics complex

Aromatics isolation
Two basic steps :
separation of the non aromatics
isolation of the single components from the mixture of aromatics

Boiling points of components are very similar. Therefore it is not

easy to separate single components by fractionated rectification.

different methods of separation necessary

Aromatics isolation
Method

Goal

Precondition

Azeotrope distillation

BTX separation from

pyrolysis gasoline

High aromatics
concentration
( > 90% )

Extractive distillation

BTX separation from

pyrolysis gasoline

Medium aromatics
concentration ( 65 90 % )

Liquid-liquid extraction

BTX separation from

reformate gasoline

Low aromatics
concentration ( 20 65 % )

Crystallization by freezing

Isolation of p-xylene
from m/p-mixtures

Separation of m-xylene and

C8-aromatics before

Adsorption to solids

Isolation of p-xylene
from C8-fractions

Continuous, reversible and

selective adsorption

Azeotrope distillation
Polar additives form low boiling azeotrope with the non aromatics
Additives: amine, alcohols, ketenes, H2O
Disadvantages:
Need of high aromatics concentrations
Advantages:
Low
L
energy consumption
ti

Extractive distillation
Nonpolar additives, that decrease the volatility of the aromatics
fraction
Additives: Sulfonate, Di-, Trichlorobenzene, Polyglycol
Advantages:
Broader areas of concentrations possible
Disadvantages:
Residue needs to be redistilled

Liquid--liquid extraction
Liquid
Extraction of the aromatic fraction from the mixture with a suitable
solvent
Extraction conditions:
Solvent must be polar enough to form two separate phases during
the extraction.
Extraction using counter current flow either in mixer-settler setups
or extraction columns.
A part of the isolated aromatics is recycled into the residue of the
extraction column to eliminate the left non aromatics

Examples for liquidliquid-liquid extractions

Method

Solvent

Reaction conditions

Ud
Udex

Mono-,, Di
Mono
Di-,, Tri
Tri- or
tetraenylenglycol/ H2O

130 150 C.
C 5 7 b
bar

Tetra

Tetraenylenglycol/H2O

not available

Sulfolan

Tetrahysdrothiophendioxide (Sulfolan)

50 100 C

DMSO

Dimethylsulfoxide/H2O

20 30 C

The extract is purified by

direct distillation in a stripper
re-extraction of the solvent followed by a fractionating distillation

Liquid liquid extraction process

(UOP)

Feed: reformate, pyrolysis gasoline

Solvent: 80% tetra-ethylene glycol and 20% Carom concentrate
Similar to Udex and Tetra process

10

Crystallization by freezing
This method is used mainly for the separation of xylene isomers. To
separate m-xylene from p-xylene in a distillation one would need 800
theoretical plates. Therefore a distillation is not efficient.
separation by crystallization
Melting points:
First o-xylene is separated by
p-xylene
+13,3 C
distillation. Then the mixture is
o-xylene
- 25,2 C
cooled down to -20 C to -75 C
m-xylene
- 47,9 C

First cooling step: up to 70% p-xylene

With several heating and cooling steps : up to 99,5 %p-xylene

Adsorption to solids
Necessary property of solids : shape selectivity for
- Educts
- Transmission state
- products

Mainly used for the separation of p-xylene from mixed xylenes

11

Mechanism of xylene isomerization

Catalyst: H-ZSM5

p-xylene

m- xylene
o-xylene

Diffusion in molecular sieves

12

The ParexParex- and the IsomarIsomar-Process

The Parex-process gives p-xylene with a quality of 99,5% purity
and a yield of 95 % from a mixture of xylenes. It uses molecular
sieves as the adsorption medium
medium.
Absorption is done at 120 175 C in the fluid phase
Desorption is done by washing with toluene or p-diethyl benzene
The Isomar process turns the residue of C8-molecules
molecules (meta and
ortho xylene) into an equilibrium of xylene isomers which can be
recycled in the Parex process.

Parex--process
Parex

13

Isomar Process

Typical Parex
Parex--Isomar Loop

14

Conversion of aromatics
Main methods of conversion
Hydrodealkylation of toluene
Isomerization of m-xylene
Disproportionation of toluene
Transalkylation of trimethylbenzens
Methylation with methanol

Hydrodealkylation of toluene (1)

Hydrodealkylation is the cleavage of side chains from aromatic
rings with H2

(H = - 126 kJ/mol)

Thermall reaction:
Th
ti
580 800 C
Catalytic reaction: 550 650 C with Cr-, Mo- or Co-oxides
Recently: 400 480 C with Re/Al2O3 as catalyst

15

Hydrodealkylation of toluene
Due to the high reaction temperatures the catalyst deactivates
quickly
CH4 formed (250 Nm per ton toluene) necessitate its separation
from the recycled gas.
conversion of methane via steam reforming to syngas
Thermal processes reach 95% purity of benzene with 60 90%
conversion of toluene
Catalytic processes on the other hand reach 99,9% purity, which
equals the costs of the catalyst.

Isomerisation of mm-xylene
Thermodynamic equilibrium at 200 500C (in wt.%) :
Ethyl benzene
o-xylene

8
22

m-xylene
p-xylene

48
22

Main processes for isomerisation:

Catalytically over Pt/Al2O3SiO2 under H2 (400 500 C, 10 25
b )
bar)
Under cracking conditions with Al2O3SiO2 (400 500 C, 1 bar)
Friedel-Crafts-Isomerisation in liquid phase with HF BF3 (100 C,
1 bar) or on Zeolites (different conditions)

16

Disproportionation and Transalkylation

Disproportionation

Transalkylation

17