Options for improving sulphonation

A Technical intervention supporting Eco Industrial Development

Working paper III

Prepared by

Centre for Environment Education

& Naroda Industries Association

Submitted to:

United States- Asia Environmental Partnership, Mumbai /

United States Agency for International Development,
as part of the project titled
‘Synergizing Industrial Production and Environmental Protection Efforts Supporting
By-product /Waste Exchange at Eco-Industrial Estates’.

October 2003

CEE
Centre for Environment Education Naroda Industries Association
The Centre for Environment Education (CEE) plays a pivotal role in nation wide efforts to create
environmental awareness. The Centre is supported by the Ministry of Environment and Forests,
Government of India and affiliated to the Nehru Foundation for Development.
The Naroda Industries Association (NIA) is the forum of industries located in the Naroda Industrial
Estate, through which several collective administrative, scientific and other initiative are coordinated.

The present project on EIN (Grant No. G2003-003-IN) is jointly coordinated by CEE and NIA.

2003
The EIN Team
Project Coordinators :Dr. R. Gopichandran1, Shailesh I. Patwari*
Research :Jigar Deliwala1, Rasesh Kotdawala1 Dr. R. Gopichandran,
Praveen Prakash1, Shalin Shah*,, Darshana Patel1
Text :Dr. R. Gopichandran, Rasesh Kotdawala, Jigar Deliwala, Shalin
Shah, Darshana Patel and Praveen Prakash
Secretarial Support : A.K. Mary1
1
CEE
* Represent Naroda Industries Association

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Contents
• Abstract
• Introduction
• Drawbacks of poor sulfonation
• Case of Naroda Industrial Estate.
• Summary of roundtable on sulfonation
• Presentation of Dr.Kanetkar on sulfonation - Annexure
• Reference

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Abbreviations

(NH4)2SO4 Ammonium sulfate

Al2(SO4)3 Aluminium Sulfate (Alum)
ASC Acetyl Sulfonyl chloride
DASA 4,4’Diamino Sulphanilide
DASDA 4, 4’ Diamino Stilbene 2,2’ Disulphonic acid
FeSO4 Ferrous Sulfate
HCl Hydrochloric acid
H2SO4 Sulfuric acid
MgSO4 Magnesium Sulfate
MnSO4 Manganese Sulfate
NIA Naroda Industrial Association
NIE Naroda Industrial Estate
PNT Para nitro toluene
PNTOSA Para nitro toluene ortho sulfonic acid

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Abstract

Capacity building of firms as part of Eco Industrial Development includes imparting abilities to
diagnose processes with reference to inadequacies in operations, with reference to immerging trends in
waste minimization and cleaner production. This paper in a series of six highlights opportunities for
reducing / eliminating acidic wastes predominantly from sulfonation processes. We examine the case
of DASA, DASDA, Fast bases and Sulfo tobias acid and relate opportunities for improvement with an
analysis of procedures considered appropriate for sulfonation with minimum waste.

An overview of less polluting sulfonation procedures is presented to provide a baseline for improved
sulfonation and accordingly identify improvement opportunities in the longer run.

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Introduction

Sulphonation is the direct introduction of sulphonic acid group. It is a very important reaction in the
chemical industry. Technology of Sulphonation is very complex due to the diversity of the feedstock
and products required. An acceptable sulphonation requires sulphonating agent, an adequate cooling
system and a good agitation and mixing system for maximum conversion of reactants to product

Oleum sulfonation* is the special case of sulfonation with H2SO4. The sulfonation reaction stops when
the acid concentration in the reaction mixture drops to less than approximately 90%. Currently sulfuric
acid sulfonation is principally used for production of hydrotropes by azeotropic reaction with benzene,
toluene or xylene. In this special process, the water formed during the reaction is removed by
azeotropic distillation of the water and unreacted feedstock. The water is then separated from the
immiscible organic feedstock, which is returned to the reaction vessel. Because water is removed, the
reaction may continue to completion.

The air/SO3 sulfonation process* is a in which SO3 gas is diluted with very dry air and reacted directly
with the organic feedstock Liquid SO3 or SO3 produced by burning sulfur is the main source of SO3.
The reaction of gaseous SO3 with organics is rapid and stoichiometric. There is a possibility of side
reactions and therefore strict process control is essential. In addition, it requires expensive precision
equipment and highly trained operating personnel.

Drawbacks of poor sulphonation

Sulphonation reactions are used to make a diverse range of products like dyes and color intensifiers,
pigments, pesticides and organic intermediates. Traditionally, sulfuric acid, oleum and chloro sulfonic
acid is used as a sulphonating agent. Dilute sulfuric acid generated after sulphonation reaction is
hazardous pollutant and its disposal is very difficult process. It is common practice in almost all
industries to neutralize dilute sulfuric acid generated after sulfonation. Neutralization generates large
quantity of solid waste (gypsum). This can be used only after meeting standard criteria for color,
organic impurity and amount of salts present. If it doesn’t meet the criteria then disposal of this waste
becomes a very big problem. Hence it is necessary to optimize sulphonation reaction to reduce amount
of spent acid or use of any new technology for sulfonation, which can eliminate problem of spent acid.

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 Case of Naroda Industrial Estate

About 26% of the industries located in the estate are engaged in the Dye and Dye Intermediate
production. Sulphonation reaction is used for the production of different types of products. DASA
(4,4’ Diamino Sulfanilide), DASDA (4,4’-Diamino Stilbene 2,2’- Disulfonic acid), Fast bases, tobias
acid are some examples which are studied for sulfonation. Different sulfonating agents used in the
estate are sulfuric acid, oleum, chloro-sulfonic acid, thionyl chloride etc. Details of sulfonation
reaction for these products are given below.

1) DASA (4,4’ Diamino Sulfanilide)

Production of DASA involves sulfonation of acetanilide using chloro-sulfonic acid.

Flow diagram for sulfonation

Chloro sulfonic acid is charged from the storage tank into

Chloro reactor at 20oC in 2 hrs. Acetanilide is added manually that
Chloro sulfonation takes 7-8 hrs. This process forms Acetyl Sulfonyl Chloride
sulfonic acid (Reactor)
Acetanilide (ASC). Temperature (55oC) is maintained for 5 hrs.
Temperature reduction (30-20oC) is obtained by circulating
cooling water/chilling water. Total process time is about 17-
18 hrs.

HCl (approx. 350 kg, scrubbed in water

and reuse)
Isolation of ASC mass is carried out in drowning vessel
Ice Isolation with ice (six phases). Reaction temperature (0-10oC) is
maintained to prevent decomposition of ASC. Process time
(including all phases) is 6-7 hr.

Filtration After isolation, ASC mass is passed through nutch filters.

Water (neutch filters) This process takes about 10-12 hrs. Spent acid is collected
in storage tank.

Spent acid (10-15%) for neutralization

Stoichiometry
NHCOCH3 NHCOCH3

2ClSO 3H + + HCl + H2SO 4

SO 2Cl
Chloro
Sulfonic Acetanilide (ASC)
Acid

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The following table presents the material balance of sulfonation of acetanilide with chloro sulofnic
acid, which generates HCl and H2SO4 as spent acid.

Chlorosulfonic Acetanilide ASC HCl H2SO4

Acid (kg) (kg) (kg) (kg) (kg)
Mole.Wt. 116.5 135 233.5 36.5 98
Stoichiometric 3366 1950 3373 528 1416
Reuirement (100%
Conversion)
But Conversion is 2693 1560 2700 422 1134
80%
Actual addition 8200 1950 --- --- ---
Excess addition 5507 390 --- --- ---

Excess addition of raw material is required to carry out reaction at desired conversion. Due to excess
quantity of reactants side-reactions also occur simultaneously. Material balance for side reaction is as
follows.
Reaction 2

This side-reaction occur due to excess quantity of chloro sulfonic acid.

ClSO 3H + H 2O HCl + H2SO 4

Chlorosulfonic Water HCl H2SO4

Acid (kg) (kg) (kg) (kg)
Mole.Wt. 116.5 18 36.5 98
Stoichiometric 5507 851 1726 4633
Requirement
Excess quantity --- --- --- ---

2) DASDA (4,4’-Diamino Stilbene 2,2’- Disulfonic acid)

Production of DASDA involves sulphonation of Para-Nitro Toluene (PNT) with oleum at 95 to 100oC.

Flow diagram for sulfonation

Sulfonation PNT (1200 kg) is charged in the sulfonator through

PNT vacuum pump. Oleum (2400 kg) is transferred from
Oleum calibration tank. Live stream is applied to maintain
Live steam the reaction temperature of 90oC.

After sulfonation, isolation is carried out by water

Water (approx 2400 lit). After this isolation, para nitro
Isolation toluene sulfonic acid (PNTOSA), formed by
sulfonation is taken to filtration.

After isolation, mixture is filtered through neutch

Filtration filters and passed through centrifuge. This
Wash water
generates about 3000-lit spent acid.

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 Stoichiometry

CH3 CH3
SO3H
+ H2SO4.SO3 Sulfonation +H2SO4 + H2O
95-100 oC

NO2 NO2
Sulfuric (18)
PNT (137) Oleum (178) PNTOSA (217)
acid (98)

The following table presents the material balance for sulfonation of PNT with oleum, which generates
H2SO4 as spent acid.

Para nitro Oleum PNTOSA H2SO4 H2O

toluene (Kg) (Kg) (Kg) (Kg)
Mole.Wt. 137 178 217 98 18
Stoichiometric 1200 1559 1901 858 158
Reuirement (100%
Conversion)
Actual addition 1200 3140 2400 1729 317
Excess addition - 1581 - - -

Excess addition of raw material is required to carry out reaction at desired conversion. This has
resulted in the generation of dilute sulfuric acid (55-60%).

3) Fast Scarlet G Base

Production of Fast Scarlet G Base involves sulfonation of Ortho-Toluidine (O.T.) with sulfuric acid as
sulfonating agent. Nitration is carried out with mixed acid (H2SO4 + HNO3). After nitration large
amount of dilute sulfuric acid (spent acid) is generated as a result of excess addition of sulfuric acid.

Flow diagram for sulfonation

Conc. H2SO4 (98%, 1750 lit) is charged in reactor

H2SO4 through pumping (7.5 Hp motor) from calibration tank in
O.T. 20 to 30 minutes. O-toluidine (400 kg) is charged after
Cooling water Sulfonator sulfuric acid addition from drum through tap at certain
Electric energy rate in 5-6 hrs. Sulfonation reaction is exothermic so
cooling water is circulated to maintain 40oC temperature.
Cooling water recycled
Sulfonated mass for nitration
Mixed acid Conc. H2SO4 (98%, 1000 lit) is charged in reactor
H2SO4 preparation through pumping (7.5 Hp motor) from calibration tank in
HNO3 20 to 30 minutes. HNO3 (60%, 375 lit) is added slowly
through carboys, which takes about 8-10 hrs. Cooling
water is circulated to maintain the temperature.

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 After sulfonation, sulfonated mass is transferred to
Sulfonated mass Nitration nitration through compressed air pump (7.5 Hp
Mixed acid motor) in 20 minutes. Mixed acid (1:3) is added at a
Elec. Energy certain rate into the mass. This reaction is highly
Chilling water exothermic, so chilling water is circulated to
maintain process temperature of 0-2oC. Total process
time is about 30-36 hrs.
Chilling water recycled

Nitromass Isolation is carried out in two reactors. First water (1000

Water Isolation lit in each) is taken into reactor in 5-10 min and
Elec. Energy temperature is raised up to 10oC. After getting 10oC
Chilling water temperature, nitromass is taken in both the reactors.
Chilling water is circulated to maintain the temperature.
Total process time is 12-15 hrs.

Neutch filter It takes about 1-2 hrs to separate solid & liquid streams

Spent acid to storage tank

Nitration:

CH3 CH3

NH2 NH2
+ H2SO4 + 2 H2SO4
(98)
+ HNO3
(63)

SO3H NO2
O.T. Sulfate Nitro mass
(187) (152)

The following table presents the material balance for nitration of ortho toluidine sulfate with sulfuric
acid, which generates H2SO4 as spent acid.

Ortho H2SO4 HNO3 Orhto H2SO4 H2O

Toluidine (Kg) (Kg) toluidine (Kg) (Kg)
(Kg) sulfate (Kg)
Mole.Wt. 107 98 63 187 98 18
Stoichiometric 400 734 234 - - -
Reuirement (100%
Conversion)
Actual addition 400 2750 375 700 4500 209
Excess addition 2016 141 - - -

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¾ Sulfo Tobias acid

Sulfo Tobias acid is produced by sulfonation of Tobias acid using oleum as sulfonating agent.

SO3H SO3H
NH2 NH2
+ H2SO4.SO3 + H2SO4

SO3H
Tobias acid (223) Oleum (178) Sulfo Tobias acid (303) Sulfuric acid (98)

The following table presents the material balance for sulfonation of tobias acid with oleum, which
generates H2SO4 as spent acid.

Tobias acid Oleum Sulfo H2SO4

(Kg) (Kg) tobias acid (Kg)
(Kg)
Mole.Wt. 223 178 303 98
Stoichiometric 700 559 - -
Reuirement (100%
Conversion)
Actual addition 700 2100 951 1848
Excess addition - 1541 - -

Characterization of spent acid generated in all processes

Sr. Name of product Sulfonation of Acidity Impurities

No. (as H2SO4)
Organic Inorganic
1 DASA Acetanilide 24% 1% -
2 DASDA PNT 60% 1% -
3 Fast scarlet G base OT 50% 4% -
4 Sulfo tobias acid Tobias acid 45% - -

Characterization of spent acid shows avg. acidity (as H2SO4) is 20-60% and organic impurity is approx
1-5%. Color of spent acid varies from dark brown to black.

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Problem

Generation of dilute sulfuric acid (spent acid) is the main problem in sulfonation processes used in the
industry.

The cause of generation in almost all cases is excess addition of sulfuric acid for sulfonation. Excess
sulfuric acid is added to facilitate mixing due to low solubility of product in the reaction mixture and
thereby completion of reaction. This acid can be utilized provided the salts, color and concentration
(strength) of the acid is in appropriate limit.

Spent acid of higher concentration (40 to 55%) is used for the purposes of neutralizing alkaline waste
streams. Spent acid of strength 10-25% is neutralized and gypsum is produced. Gypsum is further
dried and used as raw material in cement industry. However, spent sulphuric acid has some organic
and inorganic impurities and sometime having color. Due to these impurities, gypsum of inferior
quality is generated and is not used in cement industry. Storage of gypsum requires large space and
during monsoon production of gypsum is stopped.

To avoid this problem sulfonation with least generation of spent acid should be adopted by the
industrialists.

Suggestions
Source reduction
ƒ Use of appropriate quantity of sulfuric acid
ƒ Modify mixing system by putting suitable impeller and baffles to facilitate mixing
ƒ Use of liquid SO3 instead of H2SO4 and oleum for sulfonation.
ƒ Use of H2SO4 as a solvent and ionic fluid & CO2/H2O at a super critical condition
ƒ Add suitable solvent to dissolve product rather than acid

Value addition to waste

Strength of spent sulphuric acid is important factor because value addition is easy in the case of higher
strength spent sulphuric acid. Hence as far as possible industries must try to generate higher strength
of spent sulphuric acid and avoid dilution of it in any further step. Impurity in spent sulphuric acid is
another important factor in value addition. Many times spent sulphuric acid is rejected because of
color or other impurities.

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ƒ Gypsum generation
ƒ Reconcentration and reuse
ƒ Generation of sulfates like FeSO4, MnSO4, MgSO4, Al2(SO4)3, CuSO4, (NH4)2SO4 etc
ƒ Recycle and reuse in processes like rearrangement, isolation, separation, reduction etc
ƒ Neutralization of alkaline streams

Summary of roundtable on sulfonation

As part of the Eco Industrial Development project information support on alternatives was considered
equally important along with an understanding of the principles of sulfonation. Dr. Kanetkar of the
University Institute of Chemical Technology (UICT), presented an overview of sulfonation of the
organic compounds. Details of the overview are presented in the following. This includes Features of
the acceptable sulfonation reaction, Environmental impact of the H2SO4 Sulfonation, Comparison of
Batch process and continuous process, Sulfuric acid recovery including removal of organic impurities
and resinous material and tarry mass. Upgradation of recovered sulfuric acid through a three-stage
concentration process, passing of dilute sulfuric acid through electrolyzers and successive evaporation
and repeated purification were also proposed.

Under the project Eco Industrial Development, Naroda Industries Association (NIA) and Centre for
Environment Education (CEE) organized roundtable on “Advances in Sulfonation” on 26 August
2003. Chairman of GPCB Mr. K.V.Bhanujan was the chief guest. Dr. V.R.Kanetkar (Head of Dyestuff
Division, UICT, Mumbai) was invited as a chief speaker. He gave presentation on different aspects of
sulfonation along with sulfonation with SO3 gas by giving some case examples. Summary of
presentation is given in the paper.

Objective of the roundtable was dissemination of information on advance techniques available for
sulfonation amongst industrialists specifically engaged in production of Dyes & Dyes intermediate
with sulfonation as main reaction in the production. Students and professors of different engineering
colleges were also invited for the programme. Out of 110 invitees about 90 were present for the
roundtable. List of participants is given in the table below. Discussion session after presentation was
very informative and useful to the industrialists. Some important aspects of sulfonation with SO3 gas
were also discussed.

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Norman C.Foster (Ph.D., P.E. from Chemithon)* described various commercial techniques for the
production of detergent based sulfonates and sulfates by using SO3 gas. SO3 can be effectively utilized
for the sulfonates because carbon –sulfur bond in this case is more stable than oxygen-carbon-sulfur
bond formed in the sulfation. This stability difference in the products of reaction with SO3 also has a
profound impact on the choice of process used to produce sulfonates or sulfates. Some processes,
such as oleum sulfonation, cannot be used to make alcohol sulfates containing a low level of inorganic
sulfate. However others, such as sulfamic acid sulfation, cannot be used to make sulfonic acids.

Sulfur trioxide is an electrophilic reagent and easily reacts with any organic compound containing
electron donor group.

Practical problems of SO3 sulfonation

ƒ Sulfonation with SO3 is rapid and highly exothermic reaction, which releases approx. 380 KJ/Kg
SO3 reacted.
ƒ Due to heat evolution most organic compounds forms black char on contact with pure SO3.
ƒ Effective cooling is required because high temperature promotes side reactions that produce
undesirable by products
ƒ High viscosity of the formed products reduces the heat transfer coefficient from the reaction mass
ƒ Precise control of molar ratio of SO3 to organic is required to suppress formation of by products

Diluting and or complexing the SO3 to moderate the rate of reaction have solved all these problems of
the SO3 reactivity. Commercially used diluting / complexing agents are ammonia (sulfamic acid),
hydrochloric acid (chlorosulfuric acid), water or sulfuric acid (sulfuric acid or oleum) and dry air
(air/SO3 film sulfonation).

* www.chemithon.com/papers_brochures/sulfo_and_sulfa.doc.pdf

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 Centre for Environment Education
Nehru Foundation for Development
Thaltej Tekra
Ahmedabad – 380 054
Phone: 079-6858002-09 Fax: 079-6858010
e.mail: cee@ceeindia.org Website: www.ceeindia.org
“CEE is supported by the Ministry of Environment and Forests, Government of India”

Naroda Industries Association

Sheth Shantilal Kapashi Hall
184 – A/1, GIDC estate, Naroda,
Ahmedabad – 382 330
Email: niaindia@ad1.vsnl.net.in Website : www.niaindia.com

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