EXECUTIVE SUMMARY
0.1 World over, Toluene is produced from the three main sources viz.
Catalytic Reforming of Naphtha, Steam cracking of Naphtha and Coal
(Coke-oven light oil redistillation). The predominant source being the
Catalytic Reforming of Naphtha, Aromatics Extraction and Splitting
through an Integrated Aromatics Complex where Toluene is produced
alongwith Benzene or Xylenes as a by-product. The production from coal
has been on the decline.
0.2 There are two standard specifications internationally accepted for
manufacture of Toluene viz. Nitration Grade Toluene (ASTM D-841-85)
and Industrial Grade Toluene (ASTM-D-362-84). Nitration Grade Tolu-
ene is of high purity (>99.8%) and has more stringent product specifica-
tions.
0.3 In India only a small quantity (7 to 8 Thousand T/Yr) of Toluene is
produced by samll producers and the Steel Plants, bulk of the Toluene
is produced at three Refinery locations i.e., IOC, Gujarat Refinery,
Baroda, BPCL Refinery at Bombay and CRL, Cochin through the
Reforming of Naphtha, Aromatics Extraction and Splitting route. In the
year 1992-93, total Toluene production in the country was 56,900 MT,
of which 48,700 MT was produced at these three refineries and the rest
from Steel Plants and other small producers.
0.4 The demand of Toluene is now increasing moderately in India at the rate
of about 8%. The Toluene demand by year 2000/2001 is expected to
increase to 105,000 T/yr from 1992-93 demand of about 57,000 T/yr.
0.5 The total Installed production capacity for Toluene at the three refinery
locations and steel plants is approximately 55,000 T/Yr and the (actual)
current capacity is of the order of 65,000 T/Yr. (Steel plants produce
Toluene much below their currently stated capacities). Since no new
Toluene Production Unit is presently under planning or implementation
stage, it would be necessary to add additional production capacity of the
order of 40,000 T/Yr between 1994 to year 2001 in a progressive manner
(xv)
to cope up with the domestic demand or else meet the deficits through
imports.
0.6 The production of Toluene so far has been more or less matching with the
consumption with marginal, occasional imports. After the new capacity
additions at BPCL in 1985 and CRL in 1989 the production capacity was
in excess of the demand with the result that the imports during the last
few years were nil or very nominal.
0.7 With the present industrial policy and import duty reduction on
Toluene, the imports of Toluene are likely to increase in the coming years.
0.8 With new regulations restructing both Benzene/Toluene content in the
Motor gasoline, Toluene in future is likely to be surplus in the world
market, thereby increasing the market competitiveness. The export
potential is expected to be virtually nil in view of no spare capacity.
0.9 Toluene has three principle uses : (i) As a Motor spirit blending
component to boost the Octane Number (ii) as a Solvent/Thinner, for
production of dyes (iii) chemicals derived from Toluene. The important
chemicals derived from Toluene are TNT used as Explosive, Toluene Di-
Isocynate (TDI) used in Urethane Polymers; Toluene Sufonamide used as
Sacchrin (sweetener); Benzyl Chloride for Plasticizer; Benzoic Acid for
production of Phenol, Caprolactum and Terephthalic Acid; Chlorinated
derivatives for Dyes, Pesticides, Pharmaceuticals and miscellaneous
derivates used in medicines, perfumes, flavours, germicides etc.
In US, Japan and Europe a large proportion of Toluene produced is used
in Motor spirit blending and conversion to Benzene through the Hydro-
Dealkylation (HDA) process.
0.10 In India Toluene is mainly used as solvent/thinner, for dye manufacture,
chemicals production and TNT production for Defence. Small quantities
are also used for the manufacture of Pharmaceuticals, pesticides,
printing inks, magnetic tapes, saccharin, adhesives. Amongst chemicals
are included Benzoic Acid, Benzyl Chloride, Para Toluene Sulfonic Acid
(PSTA), Toluene Di-Isocynate (TDI), Toluene Sulfonamide, adhesives,
(xvi)
plastic coatings, lacquers etc. Chlorinated derivatives, Nitrotoluene,
and Pesticides do not show significant growth in India. Use of Toluene in
TDI production is expected to increase.
0.11 The export of Toluene from India has been nil mainly because it is priced
quite low in the international market. The domestic price of Toluene is
much higher due to higher basic price of the feed stock (naphtha).
0.12 Toluene is generally produced as a co-product alongwith Benzene in a
B/T production unit or in an integrated B/T/X Aromatics production
unit. Therefore the economics about the scale of plant will be mainly
governed by either Benzene or Xylenes production. The report of
Committee on Perspective Planning of Petrochemical Industry (1986}
recommended minimum economically viable production capacity of
100,000 MTPA of Benzene and 18,000 MTPA of Toluene. This would
require to set up a Catalytic Reformer of about 2,00,000 MTPA (MIN)
capacity, though this would depend on the feed composition and B/T
precursers.
0.13 Toluene produced from the Reforming of Naphtha is the most predomi-
nant source of its production world over. This involves Naphtha Hydro-
Treatment (NHT) for desulfurisation of Naphtha and Catalytic Reforming
Process for conversion of Paraffin and Naphthenes to Aromatics. A
Solvent Extraction Process is then employed for extraction of Aromatics,
which are further separated to Benzene, Toluene and Xylenes, as
required.
0.14 Naphtha Hydrotreatment section is designed to remove harmful com-
pounds from feed Naphtha stock like Sulfur, Nitrogen and Metals which
takes place over a Co-Mo or Ni-Mo Catalyst at elevated temperature and
pressure in the presence of Hydrogen. Main processes marketed are
those developed by IFP, UOP, Engelhard, Shell, Esso, Standard Oil, IFP/
IIP etc.which reduce the sulfur content of Naphtha from 200 to 1000 PPM
to 0.5 - 0.1 PPM level.
0.15 A number of catalytic reforming processes have been licensed for both
semi-regenerative and cyclic regenerative (swing reactor type) reformers.
Over the years Mono-metallic Catalysts have been gradually replaced by
(xvii)
Bi-metallic or Multi-metallic catalysts for higher severity operations and
better catalyst stability. Many processes implemented today include :
Platforming (UOP), Powerforming (ESSO), Houdriforming (HOUDRY),
Magnaforming (Engelhard, ARCO) Rheniforming (Chevron), Cat. Re-
forming (IFP, Engelhard, Kellog etc.). Variants obtained by combining
with other processes or intended for specific applications being ISO-Plus
Houdriforming (HOUDRY), Selectoforming (Mobil) Aromizing (IFP), Aro-
matic Reforming (Chevron) etc.
The recent developments in technology of Catalytic Reforming has been
the Continuous Catalyst Regenerative Reforming processes developed by
UOP (CCR Platforming) and IFP (OctanizingTechnology), which operate
on continuous withdrawal and regeneration of catalyst from the system.
This technology is specifically suited for production of Aromatics as more
severe operating conditions can be applied for higher conversion of
Paraffins and Naphthenes to aromatics. Future trend would be to go in
for such type of units.
In India two CCR type Reformers are being planned at IOC, Mathura and
Panipat Refineries.
0.16 A number of Solvents and Solvent Extraction Process have been used for
extraction of aromatics from aromatic rich streams. Most commonly
used and popular process is the "Shell Sulfolane Extraction" employing
Sulfolane as the solvent. Because of lower Solvent: Feed ratios and the
resultant lower utilities cost involved, this process finds favour. Other
Solvent Extraction Processes that have been used are Udex Process
employing Diethylene/Triethylene or Mixed Glycols as the solvents
(originally developed by Dow and licensed by UOP); the LURGI Arosolvan
process employing 'NMP' as the solvent; IFP Aromatics Extraction
Process employing 'DMSO* as the solvent.
0.17 The EIL/ IIP Sulfolane Extraction Process j ointly developed by Engineers
India Ltd. and Indian Institute of Petroleum has been successfully used
both at BPC and CRL with very good performance results. This is a
shining example where indigenously developed technology in Aromatics
Extraction has been found at par with the similar technologies currently
used in the industrialised countries of the West.
(xviii)
0.18 Splitting of Aromatics to individual compounds i.e., Benzene, Toluene,
Xylenes is carried out through a series of splitting columns using
conventional design procedures for distillation columns for the desired
purity levels. No special Process Licensing or Technology Selection is
involved therein.
0.19 Toluene is also produced in Steel Plants, where coal carbonisation in
Coke Ovens yields light-oil rich in Aromatics. Toluene yield from light oil
being in the range of 12 to 14 % volume. Light oil is recovered from coal
gases either by adsorption on solids like activated carbon or by counter-
current absorption in a high boiling liquid, which is stripped by steam
distillation. Fixed bed catalytic processes "LITOL" for purification of
Light Oil to produce high purity Benzene/Toluene has been developed by
Houdry Process and chemical co.
0.20 Substantial quantity of Toluene is present in the pyrolysis gasoline
obtained as a by-product in steam cracking of naphtha for olefins
production. The pyrolysis gasoline is selectively hydrogenated to remove
olefins/di-olefins and then catalytically treated to desulfurize the stock.
Thereafter the normal extraction of Aromatics by Solvent Extraction and
Splitting is carried out for separation to B/T/X.
0.21 Production of Toluene from surplus Propane/Butane or mixed LPG is a
comparatively new technology, which can be adapted if the raw
material is priced cheap. BP-UOP-Cyclar Process selectively converts
liquefied petroleum gas to B/T/X in a single.step. A 1000 BPSD
demonstration unit set up by BP is in operation at Gangmouth at
Scotland since 1990. Toluene yield of about 43 wt% on Butane feed are
reported.
0.22 Surplus Toluene can be converted to Benzene by the Hydro dealkylation
(HDA) processes, both catalytic and thermal. The main catalytic
processes were developed by Shell with the Bextol Process, UOP with the
Hydeal technique, Houdry with Detol and BASF Process. The main
thermal processes are those marketed by ARCO and HRI with HDA
technique and Mitsubishi and Chyoda with MHC process.
(xix)
0.23 Surplus Toluene can also increase the production of benzene and xylenes
through the Transalkylation & Disproportionation (TADP) technique,
which is of recent development. The conversion to xylenes is exploited
by introduction of C-9 Aromatics alongwith Toluene in the Transalkylation
step. ARCO's "Xylene Plus" process and Toyo Rayon's Totoray Process
are both vapour phase Toluene TADP processes, (last one commercialised
byUOP).
0.24 Naphtha cut in the distillation range of 90-110°C (TBP) are rich in
Toluene precursers. All the indigenous crude oils i.e., Bombay High,
Assam and South Gujarat (Ankleshwar, Gandhar) are rich in Aromatics
precursers including that of Toluene (possessing high N + 2A). Main
source of raw material for Benzene and Toluene production in India has
been the Naphtha derived from BH Crude. It is apprehended that the
Toluene production potential may come down in case of cut in supply of
BH crude to refineries.
0.25 The three refineries producing Toluene viz. IOC(GR), BPCL and CRL
have all used surplus/redundant capacity of their existing Catalytic
Reformers and mainly added the Aromatic Extraction and Splitting
facilities for the production of Benzene and Toluene. While IOC(GR)
employs the Udex Process originally licensed by UOP, other two refineries
adopted the EIL/IIP Sulfolane Extraction Process.
0.26 It can be said that technology for the Aromatics production has been
absorbed well. All the refinery locations are producing or capable to
produce Toluene in excess of the installed capacity. By sacrificing some
Benzene production, the Toluene production in these three locations
could be further increased.
0.27 The only Continuous Catalytic Regeneration (CCR) type reformer unit
was installed at Patalganga by Reliance Industries for its xylenes
complex with UOP technology. The CCR Technology is comparatively
new and more of such plants are now being installed elsewhere. This is
an area where R&D effort can be directed by Indian research and design
Institutes. In the immediate future this technology may have to be
imported.
(xx)
0.32 Continuing R&D work in the refinement of reforming catalysts develop-
ment of Toluene Disproportionation/Transalkylation and Hydro-
dealkylation catalysts and adaption of CCR Reforming Technology
through pilot plant scale-ups should remain the thrust areas for future.
3.33 RECOMMENDATIONS
).33.1 There is need to generate additional Toluene Production capacity to the
tune of 40,000 MT per annum from 1993 till the year 2000-2001. This
can be best done in the following ways :
By debottlenecking the capacity of existing units producing B /T at
refinery locations and by widening the feed Naphtha cut range.
Tapping Toluene potential from Pyrolysis Gasoline produced in
Naphtha crackers units and extraction of Toluene from Toluene
rich streams in Aromatics Production units.
By setting up future integrated Aromatics production units for
B/T/X production. It would be difficult to justify a production unit
for Toluene alone.
By utilizing spare capacity, if any, of CAT. Reforming units being
set up at Barauni and Digboi refineries and future CCR units to be
set up at IOC Mathura and Panipat Refineries.
1.33.2 Although organisations like EIL, IIP have developed design/engineering
capabilities for process plants involved in the production of B/T/X
through fixed bed Cat reforming and Solvent extraction, design/engi-
neering capabilities need to be developed for Continuous Catalyst
Regeneration (CCR) type of cat reformers. This needs to be backed up by
adequate R&D developmental work.
).33.3 For self reliance, efficient catalyst development should remain a thrust
area for the R&D activities. Bimetallic Catalyst already developed by IIP/
IPCL for Cat Reforming should be further refined to match in perfor-
mance with the best available in the world.
(xxii)
0.33.4 R&D efforts should be continued by IPCL/NCL for development and
commercialisation of HDA Catalyst and Toluene Transalkylation and
Disproportionation Catalysts. EIL should develop design/engineering
capabilities for commercialization of these technologies.
0.33.5 Solvent Sulfolane now widely used in aromatic extraction is being
imported. IIP, Dehradun have developed technology for its manufacture,
which could be commercially exploited.
(xxiii)
