Course: Chemical Technology (Organic) Module IV

Lecture 2
Synthetic Detergent And
Linear Alkyl Benzene
 LECTURE 2
SYNTHETIC DETERGENT AND LINEAR ALKYL
BENZENE
DETERGENT
A detergent is a surfactant or a mixture of surfactants having cleaning properties in dilute
solutions. Commonly, "detergent" refers to alkylbenzenesulfonates, a family of compounds that
are similar to soap but are less affected by hard water.
 High detergency in soft and hard water (they do not react with Ca and Mg solution.)
 Requirement of small quantity
 Detergency action at low temperature
 Do not hydrolyses
Table M-IV 2.1: Types of Specialty Surfactants
Anionic Amphoteric Cationic Nonionic
Ether carboxylates Amphoteric acetates Amine Oxide Alkyl polyglucosides
Acylisethionates Betaines and siltaines
Phosphate esters
Sarcosinates
Sulfosuccinates
Taurates
Source: Chemical Weekly November 29, P-200, 2011.

During 40’s and 50’s the detergent market was primarily captured by the dodecyl benzene
(DDB), a product formed by alkylation of Benzene with propylene tetramer in a hard detergent
alkylation unit. It was found, however, that the branched structure of the alkyl group was
responsible for the poor biodegradability of the detergent, and the linear alkyl Benzene (LAB)
was introduced in the early 60’s have substantially replaced its counter parts.

Although Linear alkyl benzene is the major detergent being used due its low cost as derived from
petroleum feed, other surfactants used widely are fatty alcohol sulphates(FAS), Fatty alcohol
ether sulphates[FES), fatty alcohol ethoxylates (AE).

Fatty Alcohols
There has been rapid growth in the use of fatty alcohols due its low toxilogical profile and safe
use, continued substitution of soap by alcohol based surfactants in the personal care industry,

145 
 
strong sales of laundary liquids that use higher levels of alcohol based surfactants, displacement
of LAS surfactants by alcohol based surfactants, the substitution of alkyl phenol eythoxylates by
alcohol based surfactants[ Brent, 2004].the global market for fatty alcohol has shown significant
growth. Oleochemical route to alcohols starting from vegetable/animal oils and fats has
dominant share(70%) of global capacity of about 3.3 million tones synthetic alcohol produced
from petrochemically derived ethylene still continues to have a about 30% share [ Chemical
weekly, November 29,2011, p.197]

CLASSIFICATION OF DETERGENT
[http://www.princeton.edu/~achaney/tmve/wiki100k/docs/Detergent.html]
ANIONIC DETERGENTS:
The detergency of the anionic detergent is vested in the anion. The anion is neutralized with an
alkaline or basic material, to produce full detergency [Kiwi Web]. Typical anionic detergents are
alkylbenzenesulfonates. There are three kinds of anionic detergents: a branched sodium
dodecylbenzenesulfonate, linear sodium dodecylbenzenesulfonate, and soap. The alkylbenzene
portion of these anions is lipophilic and the sulfonate is hydrophilic. Two varieties have been
popularized, those with branched alkyl groups and those with linear alkyl groups. [Smulders et
al., 2002].

CATIONIC DETERGENTS:
The detergency is in the cation, which can be a substantially sized molecule. Strong acids are
used, such as hydrochloric acid to produce the CI anion as the neutralizing agent although in
essence, no neutralization takes place in the manufacturing process [Kiwi Web]. Cationic
detergents are similar to the anionic ones, with a hydrophobic component, but instead of the
anionic sulfonate group, the cationic surfactants have quaternary ammonium as the polar end.
The ammonium center is positively charged. [Smulders et al., 2002].

ETHOXYLATES: Ethoxylates are compounds that have long hydrocarbon chains, but
terminate with (OCH2CH2)nOH group. These groups are not charged, but they are highly
hydrophilic owing to the presence of many oxygen centres.

146 
 
NON-IONIC OR ZWITTERIONIC DETERGENTS: This detergent consists of no inonic
constituents which are ionically inert. The vast majority of all non-ionic detergents are
condensation products or ethylene oxide with a hydrophobe. This grop of detergents is
enormous, and the permutation endless. These are characterized by their (net) uncharged,
hydrophilic head groups. They are based on polyoxyethylene (i.e. Tween, Triton and Brij series),
Chaps, glycosides (i.e. octyl-thioglucoside, maltosides), bile acids such as DOC, lipids (HEGAs),
or phosphine oxides. Zwitterionic detergents possess a net zero charge arising from the presence
of equal numbers of +1 and -1 charged chemical groups.

BASIC COMPONENTS OF DETERGENT

 Detergent (Linear alkyl benzene sulphonate)
 Builders: Phosphate (Sodium tripolyphosphate boost detergent powder), citrates,
silicates, carbonates, zeolite
 Filters and Processing Aids: Sodium carbonate, sodium sulphonate
 Corrosion inhibitors: Sodium silicate
 Anti redeposition agent: Carboxy methyl cellulose
 Fabric Brightners: Fluoroscent dyes
 Bluing: Improve whiteners by counteracting natural yellowing tendency
 Antimicrobiol agents: Carbinilides, salicylanilides
 Enzymes: Decompose or alter the composition of soil and render the particles more easily
removable.
Some of the enzymes used in detergent are protease,amlases,liapse and celolases. The enzymes
catalyses the breakdown of chemicalds through addition of water and helps in the removal of
soils.[Saini,2001a].Polymers and enzymes play important role in improving the detergency.
Polymers help in soil removal, prevent insoluble salt incrustation work as anti-soil re-deposition,
inhibit dye transfer. Use of optical brightner enhance the brightness and whiteness. processing
aids when added to slurries of detergent powder improve stability and homogeneity of slurries
during mixing and reduce viscosity[Saini, 2001b].

147 
 
LINEAR ALKYL BENZENE
LAB basic raw material for detergent which was introduced in 60's as substitute for non-
biodegradable branched. Other surfactants are alcoholsulphate (AS), alcoholethoxylates (AE),
Secondary alkane sulphonate, and alpha olefin sulphonates. LAB is a clear colourless liquid with
characteristic odour. It is most widely used as the basic raw material for the manufacture of
synthetic detergent. The linear alkyl Benzene produced from the C10 – C13 or C11 – C14 linear
mono olefins are useful detergent intermediate and can be readily sulphonated to yield linear
alkyl benzene sulphonates. These compounds constitute the “active” ingredients of many house
hold detergents. They are surface active compounds (surfactants) which are combined with
various builders (often inorganic salts) to make up a detergent formula.
Linear alkyl benzene (LAB) is the basic raw material for production of most widely used
detergent. Linear alkyl benzene was introduced as substitute for non biodegradable branched
alkyl benzene. Process involved for LAB manufacturing is mention in Table M-IV 2.3.
Although LAB demand grew by 14% per annum during 1984-90, future demand in the country is
projected to increase at a healthy growth rate of 7-8% as against 2-4% worldwide. India and
China with huge population are the largest market for LAB
LAB manufactured in India started in 1985 by IPCL in 1985 followed by Reliance Industries,
Tamilnadu Petro products, Nirma, IOC. Application of LAB in India is mention in Table M-IV
2.2.
• IPCL., Vadodara : 50,000 TPA
• Reliance Industries Patal ganga : 1,00,000 TPA
• Tamil Nadu Petro Products : 1,20,000 TPA
• Nirma Limited : 75,000 TPA
• Indian Oil Corporation, vadodara : 1,20,000 TPA
Total: 4,65,000
Table M-IV 2.2: LAB Application in India
Application Share (%)
Consumer Cleaning Products 96.2
a. Synthetic detergents for fabric wash 90.1
Popular 68.3
Mid-Price 13.3
Premium 18.4
b. Scouring products 8.7

148 
 
 c. Liquid detergents 1.2
Industrial & Institutional Cleaners 1.3
Other Industrial Application 2.5
Non-surfactant Applications( varnish, cable 0.1
fluid oil, lubricant)
Total 100
Source: Indian Oil Corporation,(Chemical Weekly November 29, P-199, 2011).

Table M-IV 2.3: Process steps in LAB manufacture

Prefractionation To obtain C10-C14 range hydrocarbons from kerosene. (n-C10 to n-
C13 for light and n-C11to n-C14 for heavy LAB).
The LAB unit requires a very specific feed in terms of carbon number.
The prefractionation unit is designed to process a high purity C9 to C15
linear (normal) paraffin feed and to separate out a heart cut with the
desired carbon number which will range from n C10 to n13 for light LAB
and nc11 – nc14 for heavy LAB.
Hydrotreator To remove sulphur compounds from feed stock
The purpose of this unit is to remove sulfur and nitrogen from the feed
without greatly changing its B.P. If not removed, sulfur and nitrogen
would poison the sieve in the Molex Unit.
Paraffin To remove n-paraffins from kerosene by selective adsorption using
Separation (Parex molecular sieve. The UOP MOLEX process is an effective method of
process) continuously separating normal paraffins from a stream of co- boiling
hydrocarbons by means of physically selective adsorption.
The feed stock is separated into a high purity normal paraffin fraction at
high recoveries and a non-normal paraffin.
Dehydrogenation Dehydrogenation of n-paraffins to olefins.
of Paraffins This process dehydrogenates the high purity linear paraffin feed
(Pacol Process) stock from the pre-fractionation unit into the corresponding non-olefins,
suitable as feed stock for the down stream detergent alkylate unit.
Alkylation Alkylation of benzene with olefins to obtain LAB in presence of HF or
solid zeolite catalyst
This process alkylates benzene with linear olefins produced by the
Pacol unit in the presence of HF acid catalyst to yield linear alkyl
benzenes, LAB. The LAB thus produced can be readily sulfonated to
form a suitable ingredient for many household detergents. This unit
consists of three processing section :
i. Alkylation Section
ii. Fractionation Section
iii. Acid Regeneration Section

149 
 
 Prefractionation
Columns

Prefractionation
Columns

Figure M-IV 2.1: Pre-fractionation Pre-Treatment and Paraffin Separation

Alkylation Unit

LAB Sulphonation

Figure M-IV 2.2: Manufacture of linear alkyl Benzene Sulponate

150 
 
LAB BY SOLID ACID CATALYST
The conventional catalyst AlCl3, H2SO4 and HF commercially used has the disadvantage of
causing corrosion of equipment as well as waste production. There has been continuous search
for development of non corrosive solid catalyst with similar catalytic properties. Some of the
catalyst which have been developed are SiO2-Al2O3, H-,ontmorillonite, amberlyst, H-Y, H-
Beta, HM [Almeida, 1994]. World LAB capacity was around 3 million tones with nearly
85percent based on HF alkylation, 5percent on the aluminium chloride process, and 10percent on
the newly developed fixed bed alkylation. The fixed bed alkylation was first introduced on
commercial scale in 1995 in Canada by Petresa. Figure M-IV 2.3 gives details for LAB
Manufacture from Fixed Bed Technology.

Figure M-IV 2.3: LAB Manufacture from Fixed Bed Technology

151 
 
MANUFACTURING OF DETERGENTS
Detergents use a synthetic surfactant in place of the metal fatty acid salts used in soaps.
They are made both in powder and liquid form. Most detergents have soap in their mixture of
ingredients, but it usually functions more as a foam depressant than as a surfactant. Various
processes in manufacturing of detergents is mention in Table M-IV 2.4.

A synthetic detergent, a sodium alkyl sulfate called sodium dodecylsulfate, will be prepared by
reacting dodecyl alcohol (dodecanol) with sulfuric acid.

The resulting dodecylsulfate is converted to the sodium salt by a reaction with sodium hydroxide.

Table M-IV 2.4: Various Processes for Making Detergent

Powder Detergent
Slurry making The solid and liquid raw ingredientsare dropped into a large tank known as a
slurry mixer. As the ingredients are added the mixture heats up as a result of
two exothermic reactions: the hydration of sodium tripolyphosphate and the
reaction between caustic soda and linear alkylbenzenesulphonic acid. The
mixture is then further heated to 85oC and stirred until it forms a homogeneous
slurry.
Spray drying The slurry is deaerated in a vacuum chamber and then separated by an atomiser
into finely divided droplets. These are sprayed into a column of air at 425oC,
where they dry instantaneously. The resultant powder is known as ’base
powder’, and its exact treatment from this point on depends on the product
being made.
Post dosing Other ingredients are now added, and the air blown through the mixture in a
fluidiser to mix them into a homogeneous powder. Typical ingredients are

152 
 
 Soda ash (anhydrous Na2CO3), Bleach (usually sodium perborate. NaBO3),
Bleach activator (e.g. tetraacetylethylenediamine), Enzymes (e.g. alkaline
protease), Colour and perfume
Liquid Detergent
Soap premix Liquid detergent contains soap as well as synthetic surfactants. This is usually
manufacture made first as a premix, then other ingredients are blended into it. This step
simply consists of neutralizing fatty acids (rather than fats themselves) with
either caustic soda (NaOH) or potassium hydroxide.
Ingredient All ingredients except enzymes are added and mixed at high temperature. The
mixing ingredients used in the liquid detergent manufacture are typically sodium
tripolyphosphate, caustic soda, sulphonic acid, perfume and water. The
functions of these ingredients have been covered above.
Enzyme The mixture is cooled and milled, and the enzymes added in powder form.
addition

REFERENCE
1. Almeida, 1994
2. Saini,S.K. “ Synyhetic detergent powders: changing trends part I “ chemical weekly
March,20,2001a,p.149 
3. Saini,S.K. “ Synthetic detergent powders: changing trends part II “ chemical weekly
March,27,2001b,p.141 
4. Brackmann,B., Deutschland,C, Hager,Claus-Dierk, “ Versatility of derived surfactants will
propel demand for fatty alcohols” Chemical weekly August 24, 2004,p155.
5. Renaud,P. Brackmann,B “ Natural based fatty alcohols” Chemical weekly August 24,
2004,p155.
6. Smulders E., Rybinski W., Sung E., Rähse W., Steber J., Wiebel F., Nordskog A., "Laundry
Detergents" in Ullmann’s Encyclopedia of Industrial Chemistry 2002, Wiley-VCH,
Weinheim
7. http://www.princeton.edu/~achaney/tmve/wiki100k/docs/Detergent.html
8. http://www.chemistry.co.nz/detergent_class.htm
9. Chemical weekly, November 29,2011, p.197
10. Chemical Weekly November 29, P-200, 2011.
11. Indian Oil Corporation, Chemical Weekly November 29, P-199, 2011. 

153