SHARIF COLLEGE OF ENGINEERING AND

TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING

UNIT PROCESS
SUBMITTED BY:
M. Haris Amin(UET-17)
SUBMITTED TO:
Dr. Shoaib Suleman
Date Total Marks Marks Obt.
22/11/2019

REMARKS: .
 SULPHONATION AND SULPHATION
DESCRIPTION:
SULPHONATION:
• Sulfonation may be defined as any chemical process by which the
sulfonic acid group -SO2OH, or the corresponding salt or sulfonyl
halide group (e.g., -SO2Cl), is introduced into an organic
compound.

• These groups may be situated on either a carbon or a nitrogen

atom Sulfonates of the second type (e.g., RNHSO2ONa) are
termed N-sulfonates or sulfamates.

SULPHATION:
• Sulfation involves placement of the -OSO2OH group on carbon,
yielding an acid sulfate (ROSO2OH), or of the -SO4- group
between two carbons, forming the sulfate ROSO2OR.

• Sulfatoalkylation designates introduction of a sulfated alkyl group

into an organic compound.

TYPES OF SULPHONATION:
Sulfonation includes:

1. Sulfochlorination (introduction of an -SO2Cl group into an alkane

using sulfur dioxide and chlorine),
 2 .Halosulfonation (reaction of a halosulfonic acid-ClSO3H or FSO3H-
with an aromatic or heterocyclic compound to introduce an -SO2Cl
or an -SO2F group),

3. Sulfoxidation (use of sulfur dioxide and oxygen to sulfonate an

alkane),

4. Sulfoalkylation, sulfoacylation, and sulfoarylation (introduction of

sulfoalkyl, sulfoacyl, or sulfoaryl groups).

CLASSIFICATION OF SULPHONATES:
 It is convenient to classify sulfonates into four main chemical
types:
1. aliphatic and alicyclic,
2. aromatic,
3. heterocyclic,
4. N-sulfonatesor sulfamates.
 The first three types have the -SO2OH group on carbon, the
chemical nature of which determines the classification. Thus,
C6H5OCH2SO2ONa (sodium phenoxymethanesulfonate) would be
considered an aliphatic sulfonate.

USES OF SULPHONATION:
This category includes detergents, emulsifying, deemulsifying, penetrating,
wetting and solubilizing agents, lubricant additives, and rust inhibitors.
Polymeric sulfonates include dispersing agents, elastomers, water-soluble
synthetic gums and thickening agents, and ion-exchange resins which
function as strong acids with complete water insolubility, an unusual
combination of properties leading to many important applications.
SULPHONATION AGENTS:
 Sulfur trioxide and Compounds:
1. . Sulfur trioxide, oleum, concentrated sulfuric acid (803 plus
water).
2. Chlorosulfonic acid (S03 plus Rel).
3. Sulfur trioxide adducts with organic compounds.
4. Sulfamic acid.
 The sulfur dioxide group:
1. Sulfurous acid, metallic sulfites.
2. Sulfur dioxide with chlorine.
3. Sulfur dioxide with oxygen.
 Sulfoalkylating agents:
1. Sulfomethylating agents (hydroxy- and aminomethanesulfonates).
2. Sulfoethylating agents (hydroxy-, chloro-, and
methylaminocthanesulfonates;
3. Ethylenesulfonic acid).
4. Miscellaneous sulfoalkylating agents,
sulfoacylation,sulfoarylation,sulfatoalkylation.
 SULPHONATION OF BENZENE
 Sulfonation is a reversible reaction that produces benzenesulfonic acid by
adding sulfur trioxide and fuming sulfuric acid. The reaction is reversed by
adding hot aqueous acid to benzenesulfonic acid to produce benzene.(ref1)

MECHANISM OF SULPHONATION OF BENZENE:

 To produce benzenesulfonic acid from benzene, fuming sulfuric acid and
sulfur trioxide are added. Fuming sulfuric acid, also refered to as oleum, is a
concentrated solution of dissolved sulfur trioxide in sulfuric acid. The sulfur
in sulfur trioxide is electrophilic because the oxygens pull electrons away
from it because oxygen is very electronegative. The benzene attacks the
sulfur (and subsequent proton transfers occur) to produce benzenesulfonic
acid.(ref-1)
PROCESS FLOW DIAGRAM
PROCESS EXPLANATION:
 Sulphuric acid is continuously pumped from storage tank by
means of pump through pressure regulator and meter to the
sulphonator.
 Liquid benzene from storage tank is continuously fed by pump
through meter to the direct vapourizer super heater and then to
the sulphonator and the sulphonation tower.
 In the sulphonator, sulphuric acid reacts with benzene, and the
reaction mass containing 30 percent unreacted sulphuric acid
flows out continuously to the top of the sulphonation tower
which is arrange like plate column.
 The reaction mass flows downward through the tower while
further reacting with a counter current stream of benzene
vapour.
 The exit benzene water vapours are continuously discharged from
the top of tower to condenser and stratified in separator and the
benzene is returned through neutrilizing drier to benzene storage
while the benzene sulphonic acid containing 2.5-3.5 percent
sulphone and 3-4 percent of sulphuric acid, is continuouslydrawn
off at the bottom of tower.

OPTIMUM CONDITION FOR THE PROCESS:

Under optimum conditions, the reaction time for this process
has been calculated 1.5 hr at 180 degree celcius, using a seven
stage reactor and employing 10 moles of benzene per mole of
sulphuric acid.In contrast,the same process operated in
batches(see pp.311 and 371) at 160-180 degree celcius would
require 14 hr and 6-8 moles of benzene per mole reacted.Thus,
the continuous method increases by nearly ten times the
capacity of batch method.It is further estimated that the ratio
of benzene uset to benzene used to benzene reacted could be
reduced as lows as 3:1 by doubling the time of reaction .The
efficiency of the processcand be further increased by using 10
percent oleum instead of sulphuric acid, thereby reducing the
required water removal without substantially raising by-
product sulphone formation.This type of process has been used
commercially in the United States.
REFRENCE:
1. https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organic_
Chemistry)/Arenes/Reactivity_of_Arenes/Nitration_and_Sulfonation_of_Benzene