UNIT-III
Links for NPTEL Lecture
[Link]
[Link]
LINEAR ALKYL BENZENE (LAB)
Linear Alkyl Benzene is the basic raw material for the production of some of the most widely
used detergents. LAB was introduced as a substitute for non-biodegradable branched alkyl
benzene. Generally LAB accounts for one-third of the active ingredients used in detergents.
Demand for laundry detergents, dishwashers, industrial and house hold cleaners accounts for
around 70 %, 15 % and 15 % respectively of the total LABS supply. Synthetic detergent became
popular due to lower price of raw material, price stability and effectiveness and
biodegradable nature. Synthetic detergent in this stage is one of the largest chemical industry, we
can say and the synthetic, and that has been only possible because of the coming of the refinery and
the petro chemical complexion. A detergent is a surfactant or a mixture of surfactants having cleaning
property in dilute solution, commonly detergent refers to alkyl benzene sulfonate, a family of the
compound that are similar to soap, but are less affected by hard water. In case of the hard water use
of the soap, for cleaning purposes was not effective, but with the coming of the detergent improved
the cleaning process.
earlier detergent market was primarily from the sodium, dodecyl benzene sulfonate made
from benzene with propylene tetramer by Friedel Craft alkylation followed by sulfonation
It was found that detergent made from the highly branched structure of the propylene
tetramer was not easily biodegradable
later it was replaced by a LAB linear alkyl benzene, which is biodegradable in nature
Feedstock for LAB
n-paraffins derived from kerosene and benzene are the two major feedstocks for the
manufacture of LAB. n-paraffins are produced using kerosene extraction technologies but the
advent of world scale GTL plants would enable the LAB industry to utilize a more cost effective
source of n-paraffins.
Composition of LAB and its Influence in the Performance of Detergents
LAB’s properties as a surfactant depend essentially on its structure (chain length, position of
phenyl group, degree of branching of alkyl chain) and on the minor component content
(dialkylindanes, dialkyltetralins and sulphones). Light duty liquids for the use in light
household applications such as dish washing are produced from LAB with carbon numbers
between C11-C12. Heavy duty laundry applications require LAB with C12-C14. Higher carbon
numbers C16-C24 are used as lubricants, detergent additives in the form of alkyl benzene
sulphonates. The alkyl benzene sulphonate derivatives of C16 and higher have low solubility
in water and are well suited for use as lubricants and cutting fluids. For maximum foam
performance, an ideal distribution for LAB in a light duty power formulation would be a C11-
C12 mixture with a predominance of internal isomer.
Process Technology
About 85% of the world LAB production is based on HF alkylation technology, all new plants
of LAB production are based on solid bed alkylation technology. Some of the advantages of
the solid bed alkylation process are better product quality, less process equipment due to
elimination of HF which requires additional steps like HF handling, regeneration, purification
and waste treatment, less maintenance cost, less cost of material of construction.
The process of LAB manufacture involves
(a) Separation of n-paraffins from kerosene by adsorption using molecular sieve and
(b) Dehydrogenation of n-paraffins to n-olefins and coupling of these olefins with
benzene in the presence of catalyst.
Various steps involved in the manufacture of LAB based on paraffins from kerosene and HF
alkylation technologies are
Prefractionation Unit
In this unit, a heart cut containing nC10-nC13 for light LAB and nC11-nC14 for heavy LAB is
obtained by fractionation of n0paraffin cut separated from kerosene.
Hydrogenation
This unit removes the sulfur and nitrogen compounds present originally in the petroleum
fractionation which are poisonous to molecular sieves in the molecular unit. This is done by
catalytic hydrogenation. Various reactions involved in LAB manufacture are given below in
Figure 11.7
n-paraffin Separation Unit
In this unit branched aromatic and cyclic hydrocarbons are removed by selective adsorption
of n-paraffins to ensure high biodegradability of the product. Using isooctane and n-pentane,
absorbents dissolve the adsorbed n0paraffins. The product from paraffin separation unit
containing mainly C10-C14 paraffins is fed to dehydrogenation unit for dehydrogenation of n-
paraffins to the corresponding mono olefins.
Dehydrogenation of paraffins
In this unit high purity linear paraffin feedstock are dehydrogenated to corresponding mono
olefins keeping conversion level at about 12014 % per pass to avoid the formation of branched
chain byproduct. The main reaction is the dehydrogenation of n-paraffins to form n-mono
olefins. Subsequently, dehydrogenation of n-mono olefins to n- olefins occur only to a minor
extent. About 90-92 % of the paraffin feed is converted to monoolefins. The reaction is
endpothermic. The catalyst used is spherical catalyst of stabilized platinum on aluminium
base. Temperature in the beginning is maintained around 400-480⁰C while at the end of run
is 482-505⁰C. Various process variables in the PACOL reactor are temperature, hydrogen-to-
hydrocarbon ratio, pressure, water injection and liquid hourly space velocity. Since the
dehydrogenation of linear paraffins to mono olefins is an endothermic reversible reaction,
equilibrium conversion of linear paraffins to mono olefins is favoured by high temperature.
hydrogen-to-hydrocarbon ratio which is defined as the ratio of the moles of hydrogen in the
recycle gas to the moles of hydrocarbon in the combined feed also affects the conversion of
n-paraffins to n-olefins. The decreases H2/HC ratio at constant total pressure increases the
conversion of n-paraffins to n-olefins. It also decreases the laod on the recycle gas
compressor, however, it increases coke formation. Water is added to the combined upstream
of reactor in order to stabilize catalyst activity.
In PACOL unit
Reactor Temperature : 480-490⁰C
Pressure : 2.0 kg/cm2
H2:HC ratio : 8:1
LHSV : 20
Water : 2000 ppm in combined feed
Alkylation Unit
In the alkylation unit, benzene is alkylated with linear olefins produced in the PACOL unit in
the presence of HF acid catalyst to yield LAB. The alkylation unit consists of an alkylation
section, fractionation section for separation of LAB from other hydrocarbon matter and an
acid regeneration section. The process variables in the alkylation unit are HF to hydrocarbon
ratio (approx. 2), benzene/olefin ratio (5-12), and temperature around 50⁰C, pressure does
not have any significant effect on the reaction.
Linear Alkyl Benzene Manufacture
Recent Advances in LAB synthesis
LAB production technology has advanced significantly over the past thirty years and a new
process technology and catalyst have been developed. A number of new catalysts have been
developed by UOP in the PACOL process. The first generation of catalysts in 1983 was DeH-7
catalyst. In 1999, UOP has introduced a new paraffin hydrogenation catalyst deH-11 having
various advantages over DeH-7. Another hydrogenation catalyst DeH-201 developed by UOP
allows higher equilibrium conversion (>75%) with an acceptable catalyst life as compared to
DeH-11 catalyst.
n-paraffins are conventionally produced from kerosene, the advent of world scale GTL plants
would enable the LAB industry to utilize more cost-effective sources of paraffins. This will
result in significant reduction in the cost of the projects, as there will be no need to invest in-
house n-paraffins production. A wolrd-scale GTL-based plant has been already announced.
Looking to cost effectiveness of Shell GTL n-paraffins into account, GTL technology will replace
the existing kerosene extraction technology for n-paraffin manufacture.
The conventional catalyst AlCl3, H2SO4 and HF commercially used has the disadvantage of
causing corrosion of equipment as well as waste production. Some of the non-corrosive solid
catalyst developed so far are SiO2-Al2O3, H-montmorillonite, amberlyst, H-Y H-Beta, and HM.
Some of the advantages of solid catalyst are: less process equipment and lower investment
(approx. 15% lower) due to elimination of steps linked to HF handling, regeneration,
purification and waste treatment, less maintenance cost and significant improvement in
quality.