Production of BTX

• Primarily BTX production is done through

catalytic reforming. With advent of IC engines of
high compression ratio. The quality of fuel has to
undergo changes. Catalytic reforming is the
process by which low octane gasoline is
upgraded to high octane value with the help of
catalyst. This is the major route for the
production of BTX.
• Dehydrogenation isomerisation reactions are
fast reactions, cyclisation reactions required
severe conditions. Elimination reactions are
slow reactions.
• Effect of pressure: low pressure increases the
rate of dehydrogenation, while isomerisation
is unaffected by pressure. Coking significantly
increases at low pressures.
• Except hydrogenation reactions which are
exothermic other reactions are favoured by
increasing temperature.
• Catalysts
• In reforming many reactions occur simultaneously,
hence the catalyst activity towards all these
reactions is highly important. Platinum
formulations are most widely used. These catalysts
are usually graded by the amount of platinum
deposited on bases like silica or silica alumina.
• Low platinum catalysts are non regenerative type
and they usually contain less than 0.3% platinum.
High platinum catalysts differ from the former by
increased metal content upto 0.5% and
regenerative type.
• Bimetallic formulations like rhenium platinum
are good in resisting fouling. The rugged
nature of bimetallic catalyst permits operation
at much severe conditions and tolerates
sulphur comfortably upto 20ppm.
• Although most of the feedstocks are
desulphurised to 2-5ppm sulphur content .
platinum catalysts are susceptible to sulphur
and nitrogen and these elements are kept
preferably below 2-5 ppm.
• Non noble catalysts are also in operation.
Select forming uses such catalysts based on
zeolites. These are dual function catalysts and
permit only straight chain compounds to
react. Activators like potassium enhance the
capacity of the catalyst. Other non noble
formulations are based on chromium
molybdenum cobalt etc.
• Raw naptha is mixed with hydrogen and sent
through a furnace 3. The mixture is
hydrodesulphurised by hydrotreating in reactor
R-II. This eliminates sulphur in the form of H2S
etc. and the gases are purged out in a separator
2 by releasing pressure.
• The sulphur free naptha is mixed with recycled
hydrogen and passed through a process heat
exchanger. The feed is further heated to around
500oC in furnace and the vaporised feed is sent
into reactors R1-R3 serially with intermediate
heating.
• Fourth reactor is called a swing reactor takes
the place of any of the reactors when
regeneration is to be done. Pressure in the
reactors is maintained around 15-75 bars.
Desired cyclisation reactions being slow are
carried and at severe conditions in the last
reactor where the temperature is higher by 20-
30oC, than the previous reactor.
• Catalyst is usually in 3 mm pellet form. Most
usually one furnace maintains all the coils for
different reactors. Sometimes intermediate
furnaces are provided.
• The reaction products are cooled by
exchanging heat with cold water . the gaseous
product usually hydrogen is obtained through
a high pressure releaser 1. The liquid product
is stabilised to drive off the low boiling
components as well as dissolved gases 2.
• The aromatic rich stock is then supplied to
solvent extraction system. Many solvents like
DMF(Dimethylformamide), DMSO(dimethyl
sulfoxide), ethylene glycols are good for
extraction of light aromatics.
• Extractor 3 consists of packed or plate column,
where the feed is introduced at the bottom and the
solvent is fed counter current to feed. The
temperature of the extractor is kept around 40-
50oC. In the present case extract is the desirable
product. Extract and raffinate are settled in a
settling column 4.
• Most of the reffinate is routed to extractor as
reflux. The rich extract from the bottom of the
column 4 goes to a stripper, where solvent and
aromatics are separated. Aromatics thus freed from
extract phase are contaminated with solvent. This
extract is then given water wash in column 6. BTX is
• After extraction separation of BTX into individual
components follows; the aromatic mixture
containing BTX is fractionated in column 1, 2, 3 as
shown in figure. The separation is purely guided
by relative volatility. Benzene and toluene can be
obtained as pure components by fractionation.
C8 aromatics consist of ethylbenzene,
• o, m, p xylene and are taken out as overhead
product of column 3. The heavier fraction C9 is
obtained as bottom product. The separation of
xylenes involve as elaborate proceduce.
 Disproportionation of toluene to benzene
and xylenes
• This is the modern methods to produce
simultaneously relatively more useful products
like benzene and xylenes. Transalkylation known
by the other name saves hydrocarbon wastage
and results in all xylenes, through p-xylene in less
pronouncive. The reaction is given below
• Mobils process employs zeolite catalyst treated
with rare earths to give rise the
disproportionation reaction.
• The temperature of disproportionation is around
300-350oC and toluene is kept under liquid phase
due to pressure 50-60 bars. Usually product from
disproportionation reaction shown 20-40%
xylenes, where the equilibrium concentration of
xylenes show 24% p, 54% m and 22% o xylenes.
• Figure shows the low temperature
disproportionation process xylenes obtained
from reforming unit is supplemented by
xylenes from toluene. Fresh toluene and
recycled toluene are heated and sent into low
temperature disproportionation reactor R-1.
The reactor is packed with catalyst.
• The stream is fractionated to separate non
aromatics and benzene in a benzene column
1. The bottoms from the column are again
fractionated in column 2 to separate toluene.
Which goes for recycling.
• The heavy fraction mixed with C8 aromatics
obtained from the reformate is fed into xylene
splitter 3, where p-xylene is obtained to a top
product. The heavy product from column3, is fed
into column to separate o-xylene from heavy
aromatics. Major part of over head from column
3, is mixed with toluene and sent into a low
temperature isomerisation.
• Reactor LT1, R-2. The feed in presence of
toluene is easily isomerised to a product of 95-
98% p-xylene in the stream. The reaction is
carried out in liquid phase at 300-350oC. The
product from the reactor is distilled to
separate the light fractions and sent through
the aromatic separation units for getting p-
xylene.
•
• Isomerisation of xylenes
• Isomerisation of xylenes is carried out to alter
the composition of reformates of
disproportionated xylenes. The most
important xylene being p-xylene other xylenes
are successfully converted into p-xylene by
isomerisation. ICI process employs fixed bed,
non noble metal(Fe, Co, Ni, Cu, Mo and W)
catalyst at near atmospheric pressure and
400-500oC to isomerise mixed xylenes to
maximum p-xylene.
• Figure shows the process. Mixed xylenes
stream after separation of lighter fractions in a
distillation column 1; fed into xylene splitter 2.
The overhead xylene stream is cooled,
crystallised in a number of crylstallisers to
separate p-xylene.
• The mother liquor is then passed through the
isomerisation reactor1. The outlet stream is
heat exchanged and hydrogen gas is
separated. The product stream is taken into
the fractionator 1 to separate the lighter
products in any;
• Isomerisation is done by using a number of
catalysts, like friedel crafts as well as noble
metals (rhenium, ruthenium, rhodium,
palladium, silver, osmium, iridium, platinum,
and gold;) and silica alumina catalysts.
• In the recent method developed by japan gas
chemical, xylenes are separated by HF-BF3
extractive solvent. This solvent is found to be
very effective for removing m-xylene. Once m-
xylene is removed, p and o xylene can be
easily separated by fractionation and
crystallisation.
• Alternatively antimony trichloride for
complete separation of p-xylene has also been
suggested m-xylene can be eliminated by
careful sulphonation from other xylenes.
• Production of aniline from phenol
• Phenol is catalytically reacted with ammonia
to yield aniline, as shown in figure a mixture of
ammonia and phenol is preheated and sent
into a reactor 1. The reactor effluent is
partially cooled, unconverted ammonia is
stripped off from the products in a column 2;
later purified and recycled.
• The product containing phenol, aniline and
water is distilled in two columns 3 and 4 in
series to drive of water;
• aniline is collected as overhead product from
the last column. Halcon process employs
copper salts as catalyst although silica alumina
would serve. The reaction is conducted at 200-
250oc under a pressure of 60-80 bars.
• Ammonia is in gaseous form or in and
aqueous solution of 20-30% concentration can
be used. This is a much simplified technology,
specially where low grade phenols in large
amounts are available.
• Phenol from chlorobenzene
• In this process benzene is first chlorinated to
chlorobenzene by in situ oxychlorination.
Benzene vapours enter the oxychlorinator
through a heater, which brings it to reaction
temperature. Aqueous hydrochloric acid
vapours from hydrolysis unit 4 and benzene
vapours are mixed with air and sent into
reactor 1.
• The reaction takes place over copper chloride
and some percent of di and tri chlorobenzenes
also form. The reaction mixture goes into a
column2, where unreacted benzene is distilled
off and chlorobenzene is sepatated in column3.
• The remaining mixture is hydrolysed 4 to yield
phenol and hydrochloric vapours. Hydrochloric
vapours are routed to reactor while phenol is
purified by distillations. Two distillation columns
are necessary to distill the product into
dichlorobenzene and phenol. Dichlorobenzene,
benzene are routed back to reactor.
 Dehydrogenation of ethyl benzene for
styrene
• Styrene is produced by dehydrogenation of ethyl
benzene. The reaction proceeds over a catalyst
containing fe2O3 with other metallic oxides or on
zinc oxide at 600-630oC.all these catalysts are
mixed with a small amount of potassium
carbonate, this facilitates the removal of carbon
deposits on the catalyst surface prolonging the
activity. 0.5-1% chromium oxide is mixed with
the support i.e. either iron oxide or zinc oxide.
• The reaction temperature is kept in the range of
560-600oC. Tubular reactors are used for
dehydrogenation. In the dehydrogenator the
partial pressure of hydrocarbon is kept around
0.1 bar by using a high ratio of steam to
hydrocarbon. Styrene concentration in the
product goes upto 35%. The difficulty in the end
product separation from ethyl benzene has to be
encountered in proper way. Styrene is distilled
under a high vaccum. Where the boiling point of
styrene is 54oC.
 Benzaldehyde
• It is produced by oxidation of toluene. This is
low yield process because the oxidation goes
through an intermediate stage of alcohol.
• Successive oxidations are more rapid and
create a problem for stopping the reaction.
This is tackled by using air oxidation for a short
time with selective catalyst. Typical reaction
conditions are
• However industrially oxidation is carried out in
liquid phase or in vapour phase using air. In
liquid phase oxidation cobalt acetate,
naphthenate etc. are used as catalysts. Vapour
phase oxidation uses zinc oxide chromium
catalyst or uranium molybdate, copper
molybdate on inert support.
• Liquid phase reaction takes place at 150-
250oC under a pressure of 10 bars. Air to
toluene ratio is maintained around 2 m3 per
kg toluene. Catalyst concentration of 0.02-
0.05% of toluene in feed is allowed. Under
these conditions, yields of over 90%, at a
conversion per pass of 30-35% are reported.
The reaction proceeds via free mechanism.
The main product is benzoic acid, while
benzaldehyde and benzyl benzoate are side
products.
• Toluene and catalyst cobalt acetate dissolved
in water are charged into the reactors, kept at
140-145oC under a pressure of 10 bars. Air is
fed continuously into this system. The heat of
the reaction is absorbed in external heat
exchanger. The product average 35% benzoic
acid and has to be stripped of toluene in a
steam stripping column. Toluene and others
collected are recycled back.
• Benzoic acid is obtained as a side cut to be
further purified in a finishing column. Catalyst
is collected from the bottom of the stripper
and recycled after scrubbing. Vapour phase
oxidation of toluene is carried out with air
400-500oC over zinc oxide chromium catalyst.
Vanadium pentoxide on inert material has
been also cited.
 Caprolactum
• Benzoic acid in the starting material for the
production of caprolactum. Benzoic acid is
hydrogenated ever conventional catalysts like
palladium at 170oc under a pressure of 15-20
bars. Two or three stirred tank reactors 1 in
series may be required. Conversion is about
85%. The product being cyclobenzene
carboxylic acid, this when 2 dehydrated yields
ketone as shown in the reactions.
• Solution of ketone is mixed with oleum 3 and
sent into nitrosation reactor 4 nitrosyl ion
attacks ketone forming oxime. The oxime
arranges into caprolactum due to deckman
rearrangement.
• Nitrosyl sulphuric acid is produced by
absorbing oxides of nitrogen in oleum. The
effluent after the nitrosyl reaction is diluted
with water 5 and unreacted cyclohexane
carboxylic acid is extracted with cyclobenzene
5 solvent.
• The solution of caprolactum in sulphuric acid
is first neutralised with ammonia 6 which
results in two layers, upper layer being organic
contains crude caprolactum. Caprolactum can
be purified by extraction with toluene and
washed with sodium hypochloric solution. The
solution of toluene containing caprolactum is
again extracted with water and the dilute
solution is evaporated in a falling film
evaporator to get crystalline form of
caprolactum.
 Products from toluene
• Chloro toluenes
• Ferric chloride influences profoundly in ring
substitutions, three different isomers ortho, meta,
para are obtained. Ferric chloride is good for
ortho substitution like other lewis acids. Metal
salts and metal sulphides are good in yielding para
substituted products.
• Uses of chlorotoluenes
• o-chlorotoluene is used as solvent, p-
chlorotoluene is used as an intermediate in
herbicide production, p-chloro benzaldehyde
is used in dyestuff industry. O-chloro toluene
is converted to o-chloro benzaldehyde that
has great application in dyestuff industry.
• Side chain substitution
• Photo chemical chlorination of toluene at about
100-140oC yields benzyl chloride, benzal chloride
and benzo trichlorides. Photochemical reaction is
brought out by means of 40W. fluorescent lamp
fitted centrally in the reactor. Simultaneously all
the hydrogen atoms can be substituted by
chlorine. Sometimes phosphorus trichloride or
peroxides can be used as catalysts.
• Benzylchloride benzalchloride and trichloride
are colourless liquids with pungent odour.
Benzyl alcohol, or butylbenezylphthalate are
some of the industrial compounds produced
from these chlorides. Most of these are used
for flavour or fragrances.
O-chloro toluene p-chlorotoluene

benzyl chloride benzal chloride benzo trichloride

• Sulphonation of toluene
• Oleum is used for toluene sulphonation
alternatively chlorosulphonic acid can also be
used for sulphonation. Major amount of
sodium sulphonate of toluene is used for the
production of cresol.

sodium sulphonate of toluene

• Theoretically SO2 is the best sulphonating
agent as there is no side product formation as
seen in the case of sulphuric acid or
chlorosulphonic acid.
• If the sulphonation with SO2 is carried out in
presence of sodium sulphite(Na2SO3). Usually
the reaction is carried out in three reactors
kept in series, first one operating at 0oC while
the other two operate at 30oC. Usually excess
toluene is distilled of for recycling.
• The mixed sulphonic acids are converted into
o and p cresols. The main isomer of industrial
significance is p-sulphonic acid, which is used
as catalyst in organic syntheses. P-toluene
sulphonylchloride is obtained by treatment of
sulphonic acid with PCl5, it is used in organic
syntheses, and in disinfectant formulations.

sulphonic acid P-toluene sulphonylchloride

• o-cresols
• cresols are produced for p and m sulphonic acid
isomers of toulene. Crude p and m sulphonic acid is
melted and added to molten caustic soda
containing 4 to 5 mole percent caustic potash at
350oC. Then sodium cresylates are formed. These
cresylates are extracted with water and then
decomposed with SO2 in presence of steam. Crude
cresols are finally distilled for separation
• Cresols are also used in paints and textiles.
Mixtures of cresols are used as solvents for
synthetic resin coatings such as wire enamels,
metal degreasers, cutting oils, and agents to
remove carbon deposits from combustion
engines. Other uses of cresol mixtures include
ore flotation and fiber treatment.