SULFONATION

Part #1
What is sulfonation
Types f sulfonation
Classification of sulfonates

Procedures for preparing sulfonates

SULFONATION
Sulfonation is the introduction of a sulfonic acid
group (SO3H), or the corresponding salt or
sulfonyl halide group into an organic compound.
Types Of Sulfonation Include
1.
Sulfochlorination
2.
Halosulfonation
3.
Sulfoxidation
4.
Sulfoalkylation
5.
Sulfoacylation
6.
Sulfoarylation

CLASSIFICATION OF
SULFONATES

Aliphatic and alicyclic

Aromatic
Hetrocyclic
N-sulfonates

PROCEDURES FOR
PREPARING SULFONATES
1.

Treatment of an organic compound with SO2

2.

Treatment with a compound of SO2

3.

Condensation and polymerization methods

Oxidation of an organic already containing
sulfur in a lower state of oxidation such as
RSH.

4.

SULFATION

Involves the placement of the OSO2OH group on

carbon, yielding an acid sulfate (ROSO2OH) , or of
the SO4- group between two carbons, forming
the sulfate ROSO2OH.

Sulfatoalkylationdesignates introduction of
sulfated alkyl group into an organic compound

CLASSIFICATION OF
SULFATES
Sulfated

alkanes
Alcohol sulfates
Cyclic sulfates
Sulfated carbohydrates
Sulfated nitrogenous polysachrides

SULFONATING AND SULFATING AGENTS

Sulfur trioxide and compounds

1.

4.

Sulfur trioxide, oleum, concentrated sulfuric acid (SO3 plus

water)
Chlorosulfonic acid (SO3 plus HCl)
Sulfur trioxide adducts with organic compound
Sulfamic acid

The sulfur dioxide group

1.
3.

Sulfurous acid, metallic sulfates

Sulfur dioxide with chlorine
Sulfur dioxide with oxygen

Sulfoalkylating agent

1.

Sulfomethylating agents
sulfoethylating agents
Miscellaneous alkylating agents

2.
3.

2.

2.
3.

CHEMICAL AND PHYSICAL

FACTORS IN SULFONATION AND
SULFATION

1.
2.
3.
4.
5.

When employing SO3 or its compound for

sulfonation and sulfation, important variables
determining the rate of reaction are
Concentration of SO3 in sulfonating agent
Chemical structure of organic compound
Time in relation to temperature and reagent
strength
Catalyst
solvents

CONCENTRATION OF SO3

1.
2.
.
1.
2.

To carry sulfonation and sulfation, it is

necessary to maintain the SO3 concentration
in the sulfonating agent at a certain
minimum level.
SO3 itself employed
Initial stage of sulfonation is completed
rapidly
But sulfonic acid produced react with SO3 to
formm complex
Sulfonating organic acid with SO3
Initial reaction product is acyl sulfate
Next it is converted to sulfonate

HYDRATES OF SO3

Hydrates of SO3 are usually the solution of SO3 in

water
Water has a great affinity for SO3
In this system it regarded as base which in
proportion to its concentration tend to neutralize
the acidic SO3

PROCEDURE FOR
COMPLETING SULFONATION

Use of excess acid

Physical removal of water
Chemical removal of water

CHEMICAL STRUCTURE

Aromatic hydrocarbons as a class are easily

sulfonated
Substitution of hydrocarbon ring with hydroxal
or amino groups, or with successive alkyl
groups, increases the ease of sulfonation
Halogen, nitro, carbonyl, and sulfonyl groups
make sulfonation more difficult
Ortho para directing groups facilitate
sulfonation, while meta directing groups hinder
sulfonation

TIME-TEMPERATUREREAGENT STRENGTH

To attain maximum efficiency in comercial

sulfonation the reaction time must be reduced to
minimum compatable with product yield
Reaction rate is approximately doubled by 10C
rise in temp.
Maximum reaction rate is achieved with stronger
reagent

CATALYST AND
SULFONATION AIDS

1.
2.
3.
4.
5.
6.
7.

Changing orientation
The addition of mercury changes the orientation in a
number of aromatic sulfonation reactions
The form of mercury employed is immaterial
An organic mercurial intermediate is formed
Catalytic effect functions for disulfonation
Mercury is utilized only when using oleum or SO3
as sulfonating agent.
Mercury effects the orientation of benzoic acid,
phthalic anhydride,naphthol, nitrobenzene.etc
Mercury is also utilized in some cases to increase
yield in sulfonation but without changing orientation

CATALYST

1.

.
1.

Facilitating reaction
The addition of catalyst sometimes allows the
use of lower temperatures, improve yield,
acceleration reaction.
Inhibiting side reactions
sulfone formation in case of aromatic
sulfonation can be avoided by adding acetic acid

SOLVENTS

Excess acid
Chlorinated solvents
Liquid SO2
Aqueous solvents
Miscellaneous solvents
Solvent stability

KINETICS OF SULFONATION

Aromatic sulfonation is a eelectrophilic substitution

reaction
Sulfonation is a reversible process
Reaction temperature in certain cases have an
important influence on position of entering group
Sulfur tri oxide has a tendency to form complex with
sulfonic acid
With sulfuric acid formation of water slows the
reaction
With sulfur high speed of reaction is a problem
We have different rate equations with different
sulfonating agents

MECHANISM OF REACTION

Eelectrophilic substitution

AROMATIC SULFONATION

Without sulfur trioxide

Intermediate compound is electrically neutral.

THERMODYNAMICS

Heats effects encountered in sulfonation are of

great importance.
Depending upon the reaction involved and
upon how it is conducted, net effect may vary
widely from highly exothermic over a short
period of time to endothermic over a long
period
Some reactions are exhothermic in initial stage
but endothermic in final stage.

WITH SO3 AND ITS

COMPOUNDS

1.
2.

With SO3 and its compounds it is convenient

to calculate the net heat effect in any
particular sulfonation by using SO3 vapour
as reference point reasons are
More heat is evolved in sulfonation with this
reagent then with any other group
All th compound of SO3 used as sulfonating
agents can be made from it by direct
exothermic reaction with the material
forming the compound

HEAT OF SULFONATION
Net heat evolved can be calculated from the
following equation
Hc = Hv - HD
Hc = heat of sulfonation with compound of SO3
being used as sulfonating Agent
Hv = heat of sulfonation with SO3 vapor
(exothermic)
HD = heat of dissociation of sulfonating agent
into SO3 vapor and compounding reagent
(endothermic)

DESULFONATION
REACTIONS

Aromatic sulfonates are hydrolytically desulfonated by

heating in aqueous acid medium
This reverse reaction generally proceeds in rapidly and
in good yield especially in the presence of mineral acid
which accelerates the reaction catalytically.
It is proportional to hydrogen ion activity of solution.
For each 10C rise in temperature the reaction velocity
of hydrolysis increases 2.5-3.5 times and same with
molar increase in acid concentration.
With increase ring methylation desulfonation
temperature lowers.

DESULFONATION

Sulfonation followed by desulfonation has

been used to separate mixtures of aromatic
compounds not easily separable by sulfonation.
Desulfonation is a tool in studying the
chemical structure of commercial sulfonated
petroleum fractions from lubricating oil range.
Sulfonation-desulfonation is a useful tool for
preparing ortho isomer derivative of benzene.
Useful in raw material and waste recovery

WORKING-UP PROCEDURES

1.
2.
3.
.

There are different factors that make the final

product separation a time consuming
process.
Presence of excess acid
Unreacted starting material
Occurrence of side reactions
Some commercial sulfonation apply
stoichiometric amounts of reagents and
product can be used after neutralization.
In some cases even with excess acid more
seperation is not required

SEPARATION PROCESSES
Dilution with water

1.
2.
3.
4.
5.

This method is often applied when using excess acid

or oleum and yield free sulfonic acid
Its use is based on the knowledge that many sulfonic
acid are relatively insoluble in sulfuric acid of
intermediate strength obtainable by suitable dilution
of reaction mixture with water
Applied for th separation of
Hydrocarbon sulfonic acids
Disulfonic acid of anthraquinone
Sulfonated aromatic amines
Sulfonated fatty oils
Aromatic sulfonyl chlorides

SEPARATION PROCESSES

Salting out

The method yields the sulfonate salt by the addition

of aqueous NaCl to the acid reaction mixture
The desired sulfonate salt is usually only slightly
soluble in the dilute acid medium and often
crystallizes from it in good yield.it is used in
seperation of
Sulfonate dye intermediates
Sulfonated fatty oils
Efficiently employed to obtain highly water soluble
sulfonate salts

1.
2.
3.

SEPARATION PROCESSES
Neutralization with lime

The procedure involves treatment of diluted reaction

mixture with Ca(OH)2 or CaCO3 to convert excess
sulfuric acid to insoluble calcium sulfate and the
sulfonic acid to calcium sulfonate.
Treatment of filtrate with sodium carbonate or sulfate
yields insoluble calcium carbonate or sulfate
The filtrate comprises the desired sodium sulfonate
Use for the isolation of any sulfonate yielding a soluble
calcium salt.

INDUSTRIAL EQUIPMENT
AND TECHNIQUES

Material of construction
Cast iron is resistant to action of sulfuric acid
Lined steel vessels combine low cost and high
strength with good corrosion resistance

COMMERCIAL
SULFONATION METHODS

Batch process
Continuous process

BATCH PROCESSING

Sulfonation is conducted in
autoclaves of standard type
Major
feature
of
consideration
are
heat
transfer and agitation
Depending upon conditions
equipment maay be of cast
iron,glass lineed, lead lined

BATCH PROCESSING

Ball-mill sulfonator,operable under vacuum with

hot air heating, used with solid, doughy or
viscous masses.
Plastic coated steal towers are used.

HEATING AND COOLING

Sometimes direct gas fire is used for heating

Steam is most commonly employed
Steam under pressure is used in jackets capable of
bearing 10atm pressure
In some cases cooling is required which could be
done by using brine.
By spraying water outside of kettle.
By circulating through heat exchanger

CONTINUOUS PROCESS

Continuous process in sulfonation is usually

preferable in dye intermediates which are prepared
in relatively small amount from expensive raw
materials

ALIPHATIC SULFONATION

1.
2.

3.
4.

5.
6.

Sulfomethylation of aniline
Aniline is reacted with aqueous sodium
hydroxymethanesulfonate.
Aqueous sodium bisulfite is charged to a brick lined
vessel equiped with a blde agitator and copper coil
for heating and cooling.
Formaldehyde is then added with agitation followed
by heating for half an hour.
After cooling to 25C aniline is added and
temperature is maintaind to 25C for 3
hours.followed by heating to 35C for one hour.
Tests are performed to check completion.salting out
is done to get sulfonate.
Product is washed and filtered off.

ADDITION OF SODIUM BISULFITE

TO MALEIC ACID ESTER

Di maleate and 95% and ethanol are charged to an

enameled jacketed kettle provided with moderate
agitation and distillation take off.
Aqueous sodium hydroxide is then added to neutralize
toluene sulfonic acid catalyst in the crude ester.
Aqueous bi sulfite is then added and the mixture is
heated to 100C with slow agitation.it is held at this
temp for 12 hours
The mix is cooled to 60C and the distillation take off is
connected for the removal of alcohol solvent begins at
80C
Distillation continued for 7 hours aat 91C to remove
75% alcohol.
Solution is then cooled and packed

SULFOETHYLATION OF
OLEIC ACID

Oleoyl chloride is heated with sodium

2hydroxyethanesulfonate.
Solid 2-hydroxyethanesulfonateis shoveled into a
homogeneous lead lined condensation kettle.
Heating and stirring begin with oleoyl chloride
addition.
The mixture is stirred for 15 min after reaching 100C.
When the reaction is vigorous and HCl evolved.
Temperature rises to 110C.
Finally powdered product is attained
Neutralize with sodium carbonate

MONOSULFONATION OF
BENZENE

Benzene can be monosulfonated by partial

pressure distillation method
Sulfuric acid is pumped from storage
Liquid benzene from storage is pumped to direct
vaporizer superheater and then to sulfonator and
sulfonation tower
Reaction time is 1.5 hours
Temperature is 180C

SULFONATION OF
DODECYLBENZENE

The hydrocrbon is pumped into the glass lined

sulfonation kettle equiped with turbo type mixer and
external heat exchanger.
Mixer is turned on and 20% oleum is added as fast as
possible, not exceeding a temperature of 30C.
Reaction time is 1.5-2.0 hours.
At the end spentacid has a strength of 98.2% and is
mixed with sulfonic acid
Water is added for layer seperation
Upper laayer of sulfonic acid is neutralized by adding
aqueous soda
Approximately 90% of the hydrocarbonis sulfonated.

SULFONATION OF BENZENE

Benzene can be sulfonated by;

Batch process
Continuous process
Batch time is more as compared to residence time
in continuous reactor.

BATCH PROCESS FOR

MONOSULFONATION OF BENZENE

Reaction time:14 hrs

Temperature:160-180oC
Acid strength:90-92%
Jacketed cast iron sulfonation kettle is used
Agitation done at 80rpm

MONOSULFONATION OF BENZENE BY
CONTINUOUS PROCESS

Sulfuric acid is pumped from storage

Liquid benzene from storage is pumped to direct
vaporizer super heater and then to sulfonator and
sulfonation tower
Reaction time is 1.5 hours
Temperature is 180C

BATCH PROCESS FOR MONOSULFONATION OF

BENZENE
Recycled
benzene
Benzene
feed line

Benzene
supply tank
Gaug
e
Jacket

External oil Perforated

heating
distributor
mechanism

Cooling
coil

Condensed
liquor tank

Pressure
regulator
Meter

MONOSULFONATION OF BENZENE

Benzene+
water
vap.
Sulfon
-ator

Benzene vap.

Condense
r

Separato
r
water

Benzene

Sulfonatio
n tower
Direct vaporizer
super heater
meter

Product

Neutralizing
drier

Pump

Sulfuric acid tank

Liq.Benzene
storage tanks

ANTHRAQUINONE 1-SULFONATE
Raw materials
quinone
oleum
Catalyst
Mercury sulfate
Sulfonator temp. 50-60oC
Reaction time in sulfonator:30 min

Wash water
storage

Mixe
r

AQ
dryer

Storage for rotary

filter
Filter for
recovered
anthraquinone

Rotary filter
Storage
mixer for
35%K-salt
slurry

Conc. KCl
soln.
Neutral
mixer

Storage

Sulfonat
or

Anthraquinone
80oC
crystallizer

Filtrate
receivers

85oC

Pptator
for K-salt