Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 1.5
LINEAR ALKYLBENZENE
(LAB) MANUFACTURE
Andrea Bozzano
UOP
Des Plaines, Illinois

INTRODUCTION

The detergent industry originated in the late 1940s with the advent of sodium alkylbenzene
sulfonates, which had detergency characteristics far superior to those of natural soaps.
Natural soaps are sodium salts of fatty acids obtained by the alkaline saponification of nat-
urally occurring triglycerides from either vegetal or animal sources. The early alkylben-
zene sulfonates (ABSs) were essentially sodium dodecylbenzene sulfonates (DDBSs), also
known as branched alkylbenzene sulfonates (BABSs) obtained by the Friedel-Crafts alky-
lation of benzene with propylene tetramer, a mixture of branched C12 olefins.
Dodecylbenzenes (DDBs) are then sulfonated with oleum or sulfur trioxide (SO3) and neu-
tralized with sodium hydroxide or soda ash.
Because of their lower cost and high effectiveness in a wide range of detergent formu-
lations, DDBSs rapidly displaced natural soaps in household laundry and dishwashing
applications. However, although excellent from a performance viewpoint, BABS exhibit-
ed slow rates of biodegradation in the environment and, in the early 1960s, started to be
replaced by linear alkylbenzene sulfonate (LAS or LABS). The linear alkyl chains found
in LAS biodegrade at rates that are comparable to those observed in the biodegradation of
natural soaps and other natural and semisynthetic detergent products.
The use of DDBS has never been formally banned in the United States, but by the late
1960s, its use had been largely phased out in the United States, Japan, and several
European countries. By the late 1970s, the use of LAS had become more generalized, and
new facilities were added in developing countries around the world. Currently, LAS
accounts for virtually the entire worldwide production of alkylbenzene sulfonates. The
demand for linear alkylbenzene increased from about 1.0 million metric tons per year
(MTA) in 1980 to about 1.7 million in 1990. The demand for LAB is approximately 2.5
million MTA and is growing at an annual rate of 3.5 percent as of 2002. Worldwide LAB
production capacity is approximately 2.8 million MTA as of 2002.

1.57
Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)
Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

1.58 ALKYLATION AND POLYMERIZATION

TECHNOLOGY BACKGROUND

Various routes were developed and used in the production of LAB. The first hurdle to be
overcome was the recovery, typically from kerosene or gas oil fractions, of linear paraffins
(n-paraffins) in the C10 to C14 range. Initial recovery attempts were based on the use of urea
adducts, which were soon replaced by adsorptive separation and recovery techniques, in
either the vapor or the liquid phase. These techniques used a variety of adsorbents and des-
orbents. Adsorptive separation techniques based on the molecular sieve action of 5-Å zeo-
lites have dominated this industry since the mid-1960s. Typical commercial process
technologies for this separation include the UOP Molex* process in the liquid phase with
a hydrocarbon desorbent that makes use of UOP’s Sorbex* simulated moving-bed tech-
nology; the UOP IsoSiv* process (formerly Union Carbide’s), which operates in the vapor
phase also with a hydrocarbon desorbent; Exxon’s Ensorb process, which is also in the
vapor phase but has an ammonia desorbent; or a similar technology developed in the for-
mer German Democratic Republic (East Germany) and known as the GDR Parex process,
which also operates in the vapor phase with ammonia desorbent. The GDR Parex process
is not to be confused with UOP’s Parex process for the selective recovery of high-purity p-
xylene from aromatic streams using the Sorbex simulated moving-bed technology.
Once the linear paraffins have been recovered at sufficient purity, typically in excess of
about 98 percent, they have to be alkylated with benzene to produce LAB. To date,
attempts to alkylate n-paraffins with benzene directly have failed, thus necessitating the
activation of the n-paraffins to a more reactive intermediate before the alkylation with ben-
zene can take place.
The following routes for the production of LAB emerged during the 1960s:
● Chlorination of n-paraffins to form primarily monochloroparaffins. Benzene is then
alkylated with monochloroparaffins using an aluminum chloride (AlCl3) catalyst. An
example of this route was developed and commercialized by ARCO Technology Inc.1
● Chlorination of n-paraffins followed by dehydrochlorination and alkylation of the result-
ing olefins with benzene typically using hydrofluoric (HF) acid as catalyst. Shell’s CDC
process (for chlorination/dehydrochlorination) is an example of such a process. This
type of technology was still used commercially until the mid-1980s by, among others,
Hüls AG in Germany.
● Alkylation of linear olefins with benzene also using an HF catalyst. The olefins are usu-
ally linear alpha-olefins (LAOs) from wax cracking (now discontinued), alpha-olefins
from ethylene oligomerization, or linear internal olefins (LIOs) from olefin dispropor-
tionation. Various companies, such as BP, Chevron (formerly Gulf), and Shell, offer
technologies for the oligomerization of ethylene to LAO; Shell also produces linear
internal olefins by disproportionation in its Shell Higher Olefins process (SHOP).
● Dehydrogenation of linear paraffins to a fairly dilute mixture of LIO in unconverted n-
paraffins, followed by the alkylation of the olefins with benzene also using HF acid cat-
alyst but without the separation and concentration of the LIO. UOP’s Pacol* process for
the catalytic dehydrogenation of n-paraffins and UOP’s HF Detergent Alkylate* process
for the alkylation of the LIO with benzene are prime examples of this approach. A sim-
ilar approach is also practiced by Huntsman Corp. (formerly Monsanto’s).2,3

During the early days of LAB production, paraffin chlorination followed by alkylation
over AlCl3 gained some prominence. However, since the late 1960s, the dehydrogenation
and HF alkylation route has been the most prominent because of its economic advantages

*Trademark and/or service mark of UOP.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

LINEAR ALKYLBENZENE (LAB) MANUFACTURE 1.59

and higher-quality product. Although LAO and LIO obtained from sources other than
dehydrogenation can equally be used, n-paraffin dehydrogenation routes have usually pre-
vailed because of the lower cost of the starting kerosene fractions. Table 1.5.1 shows an
approximate 2001 distribution of world LAB production employing these technologies.
The dehydrogenation followed by alkylation route accounts for 81 percent of world LAB
production. The Detal* process, which replaces HF with a solid heterogenous acid cata-
lyst, was introduced in 1995. The various routes for the production of LAB are illustrated
schematically on Fig. 1.5.1.

COMMERCIAL EXPERIENCE

The first commercial operations of UOP’s dehydrogenation and alkylation technologies

were in Japan and Spain at the end of 1968. Almost all the units built since then through-
out the world employ UOP technology. Over the years, UOP has continued research and
development and has introduced numerous improvements that resulted in improved eco-
nomics of LAB manufacture as well as consistently improved product quality. More than
30 LAB units now operate around the world with this process technology.

*Trademark and/or service mark of UOP.

TABLE 1.5.1 2001 World LAB Production by

Technology Route

Technology route Production, %

Chlorination and alkylation 10
Dehydrogenation and alkylation 81
High-purity olefins to alkylation 9
Total 100

FIGURE 1.5.1 Routes to LAB.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

1.60 ALKYLATION AND POLYMERIZATION

The new Detal process was developed jointly by UOP and PETRESA, a wholly owned
subsidiary of CEPSA in Spain. The process uses a fixed bed of acidic, noncorrosive cata-
lyst to replace the liquid HF acid used in the present UOP HF Detergent Alkylate process.
The catalyst of choice for LAB production has been HF acid since the first Pacol unit
came on-stream in 1968. Its high efficiency, superior product, and ease of use relative to
the older AlCl3 catalyst are the reasons for this success. However, in both the HF- and the
AlCl3-catalyzed processes, the handling of corrosive catalysts has had implications in
terms of the increased capital cost of the plant as well as in the disposal of the small quan-
tities of neutralization products generated in the process. Hence, the advantages of a het-
erogeneous catalyst in this application have long been recognized.
Aromatic alkylation has been demonstrated over many acidic solids, such as clay min-
erals, zeolites, metal oxides, and sulfides. Although many of these catalysts are highly
active, they are usually lacking in selectivity or stability. The key to a successful solid-bed
alkylation process is the development of a catalyst that is active, selective, and stable over
prolonged periods of operation. Research at PETRESA and UOP resulted in the develop-
ment of a solid catalyst for the alkylation of benzene with linear olefins to produce LAB.
The resulting Detal process was proved at UOP’s pilot plants and at PETRESA’s semi-
works facility in Spain and is now in commercial operation. As of today, there are three
operating Detal units worldwide and three more in the design phase. The process produces
a consistent-quality product that meets all detergent-grade LAB specifications.
The simplified flow diagrams in Figs. 1.5.2 and 1.5.3 illustrate the main differences
between the HF Detergent Alkylate and Detal processes. Figure 1.5.4 shows an integrated
LAB complex that incorporates Pacol, DeFine,* and detergent alkylation units. The flow
scheme for the Pacol and DeFine units remains unchanged for either an HF- or a solid-cat-
alyzed, fixed-bed alkylation unit.
In the HF Detergent Alkylate process, olefin feed from the Pacol-DeFine units is com-
bined with makeup and recycle benzene and is cooled prior to mixing with HF acid. The
reaction section consists of a mixer reactor and an acid settler. A portion of the HF acid
phase from the settler is sent to the HF acid regenerator, where heavy by-products are
removed to maintain acid purity. The hydrocarbon phase from the acid settler proceeds to
the fractionation section, where the remaining HF acid, excess benzene, unreacted n-paraf-
fins, heavy alkylate, and LAB product are separated by means of sequential fractionation
columns. The HF acid and benzene are recycled to the alkylation reactor. The unreacted n-
paraffins are passed through an alumina treater to remove combined fluorides and are then
recycled to the dehydrogenation unit. The flow diagram in Fig. 1.5.2 shows the HF acid
handling and neutralization section, which is required for the safe operation of the plant
and is always included within battery limits. This section represents a significant portion
of the investment cost of HF alkylation plants.
In the Detal scheme (Fig. 1.5.3), olefin feed combined with makeup and recycle ben-
zene flows through a fixed-bed reactor, which contains the solid catalyst. The reaction
occurs at mild conditions in the liquid phase. Reactor effluent flows directly to the frac-
tionation section, which remains the same as for the HF acid system except that the HF
acid stripper column and the alumina treater are eliminated. Also eliminated is the entire
HF reactor section, including the mixer reactor, acid settler, HF acid regenerator, and asso-
ciated piping. In addition, all the equipment and special metallurgy required for the safe
handling of HF acid, neutralization of effluent steams, and disposal of the neutralization
products are not required.
Because hydrocarbons such as paraffins, olefins, benzene, and alkylbenzenes are han-
dled in the Detal process, only carbon-steel construction is used. Thus, the Monel parts and
special pump seals used in HF service are eliminated.

*Trademark and/or service mark of UOP.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LAB Recycle from Recycle Column
VE
Steam

HFS

PC
RR
RC

HS

AR
BC
AS

AM

ASD
Flush

BAT
Heavy
Linear Paraffin Linear
Alkylate
Recycle Benzene to Pacol Detergent
Alkylate
Scrubbed Gas
to Flare
Linear

1.61
Paraffin-Olefin
Acid Relief
KR

PN
DD

PSD
Charge from Pacol KD
and Vents

BS
KMT
SC

Paraffin Dehydrogenation Unit

Neutralized
Heavy Alkylate
Components
Benzene Off-Spec
Charge
ASD – Acid Storage Drum PC – Paraffin Column KD – Knockout Drum
LINEAR ALKYLBENZENE (LAB) MANUFACTURE

AM – Alkylation Mixer RR – Rerun Column SC – Scrubber

AS – Alkylation Settler RC – Recycle Column KMT– KOH Mix Tank
AR – Acid Regenerator VE – Vacuum Ejector KR – KOH Regenerator

Any use is subject to the Terms of Use as given at the website.

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
HFS – HF Settler BS – Benzene Stripper
HS – HF Stripper PSD – Polymer Surge Drum
BC – Benzene Column PN – Polymer Neutralizer
BAT – Benzene Aluminum Treater DD – Degassing Drum

FIGURE 1.5.2 HF Detergent Alkylate process.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

1.62 ALKYLATION AND POLYMERIZATION

Recycle
Paraffins
LAB
Product
Recycle Vacuum
Benzene
Benzene
Feed

Olefin
Feed
Rx

HAB
Recycle Product
Benzene Paraffin Paraffin
Column Stripper Column LAB Colu
FIGURE 1.5.3 Detal process flow scheme.

Research on the Detal catalyst showed that diolefins and some other impurities, most-
ly aromatics, coming from the Pacol dehydrogenation unit have a substantial impact on the
activity and stability of the Detal catalyst as well as on LAB quality. Thus, a DeFine
process unit must be included to convert all diolefins to monoolefins. Additionally, UOP
developed technology to remove aromatics from the alkylation feed. Normally, these aro-
matics alkylate with olefins and produce a heavy alkylate by-product in the alkylation unit.
Thus, aromatics removal has two benefits: increased LAB yield per unit of olefins and
improved activity of the Detal catalyst.

PRODUCT QUALITY

Table 1.5.2 compares LAB product properties for the two catalyst systems: HF and Detal.
The quality of the two products is similar, but LAB produced from Detal units has slight-
ly higher linearity. Both processes achieve low levels of tetralins in the LAB. However, the
Detal process achieves a lower level (less than 0.5) of tetralins compared to the HF
process.
The Detal LAB product also produces a lighter-colored sulfonate. As shown in Table
1.5.2, the Klett color of a 5% active solution of Detal-derived LAS is typically lower than
that of LAS obtained by using HF.
The most significant difference between HF and Detal LAB is in the higher 2-phenyl-
alkane content of the LAB obtained in the Detal process. This higher content of 2-phenyl-
alkane improves the solubility of the sulfonated LAB. The difference is particularly
important in liquid formulations, as illustrated in Fig. 1.5.5, which shows the cloud point
of the LAS derived from both systems. Over the range of 13% to 25% active solution of
sodium LAS, the Detal derived product exhibits a lower cloud point and is much less sen-
sitive to concentration compared with the HF derived product.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

FIGURE 1.5.4 Production of LAB from linear paraffins.

1.63
Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)
Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

1.64 ALKYLATION AND POLYMERIZATION

TABLE 1.5.2 Comparison of HF and Detal LAB

Typical Typical
HF LAB Detal LAB
Specific gravity 0.86 0.86
Bromine index ⬍15 ⬍10
Saybolt color ⫹30 ⫹30
Water, ppm ⬍100 ⬍100
Tetralins, wt % ⬍1.0 ⬍0.5
2-Phenyl-alkanes, wt % 15–18 ⬎25
n-Alkylbenzene, wt % 93 94
Klett color of 5% active
LAS solution 20–40 10–30

FIGURE 1.5.5 Solubility comparison of HF and Detal LAS.

ECONOMICS

A comparative economic analysis was prepared for the production of 80,000 MTA of LAB
using either the HF Detergent Alkylate or the Detal process. The complex was assumed to
consist of Pacol, DeFine, and HF Detergent Alkylate or Detal units (with aromatics
removal in the latter) as well as a common hot-oil belt. The equipment was sized on the
assumption of 8000 h on-stream per year, which corresponds to an effective production
capacity of 240 metric tons (MT) per stream-day.
The erected cost for the complex based on the HF Detergent Alkylate process is esti-
mated at $56 million. The same complex using the Detal process has an estimated erected
cost of $45 million. All design, construction, and labor costs were estimated on an open-
shop basis for a U.S. Gulf Coast location.
The economic analysis is summarized in Table 1.5.3. The yields represent the produc-
tion of LAB with an average molecular weight of 240.
By-product credits include hydrogen at about 95 mol % purity, light ends, heavy alky-
late, and HF regenerator bottoms. Utility requirements correspond to a typical modern
design of the UOP LAB complex. The cost of effluent treatment and disposal has not been
included in this analysis.
The combined investment for the Pacol, DeFine, and the hot-oil units for the two cases is
essentially the same. The fixed plant investment for the alkylation section has been reduced

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

LINEAR ALKYLBENZENE (LAB) MANUFACTURER 1.65

TABLE 1.5.3 Economic Comparison of HF Detergent Alkylate and Detal Processes in a LAB
Complex*

HF Alkylation, Detal, per

per MT LAB MT LAB
Unit cost, $ Quantity $ Quantity $
Raw materials:
n-Paraffins, MT 480 0.78 350 0.78 352
Benzene, MT 300 0.33 99 0.33 100
By-product credits, MT — 0.33 20 — 21
Catalysts and chemicals — — 21 — 28
Utilities:
Power, kWh 0.05 283 14 281 14
Cooling water, m3 0.02 81 2 24 1
Fuel fired, million kcal 3.74 2.86 25 3.04 27
Fixed costs — — — — —
Cash cost of production — — 545 — 548
Cash flow, million $ (LAB at $850/ton) 24.4 24.2
Estimated erected cost, million $ 70.1 56.6
Simple payback, years (on fixed investment) 2.2 1.9

*Basis: Production cost for 80,000-MTA LAB.

Note: MT ⫽ metric tons; MTA ⫽ metric tons per annum.

TABLE 1.5.4 Historical Demand for LAB by Geographic Areas

LAB consumption, 103 MTA

Area 1980 2000
Europe and former Soviet Union 415 470
Africa 35 140
Middle East 30 170
Asia 280 800
Americas 290 820
Total 1050 2400
Note: MTA ⫽ metric tons per annum.

by some 15 percent. The absence of HF acid, and hence the absence of the corresponding
neutralization facilities for the acidic wastes, is reflected in a lower operating cost.

MARKETS

The evolution in the demand for LAB differs in the various geographic areas. Since the
early 1990s, these different growth rates have reflected not only the maturity of the most
economically developed markets but also the trend toward a healthier economic future.
Table 1.5.4 summarizes the consumption of LAB in various geographic areas for the years
1980 and 2000. The per capita consumption, in kilograms per year, was used to forecast
the potential expected LAB demand worldwide. Figure 1.5.6 reflects the situation in 1991
in these same geographic areas in terms of kilograms per capita per year. The data in the
table and the figure highlight the consumption trends in various markets of the world.
From these data, scenarios can be established for various parts of the world.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 Far
East
Eastern
0.7-0.8 kg/yr
Europe
North Western 0.3-0.4 kg/yr
America Europe China
0.9-1.2 kg/yr 0.8-1.4 kg/yr Mideast 0.2 kg/yr
0.3-0.5 kg/yr
North

1.66
Africa
0.4-0.7 kg/yr
India
0.2 kg/yr Southeast
South Asia
Latin Africa 0.5-0.9 kg/yr
0.1-0.3 kg/yr
LINEAR ALKYLBENZENE (LAB) MANUFACTURE

America
0.5-1.5 kg/yr

Any use is subject to the Terms of Use as given at the website.

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
FIGURE 1.5.6 Estimated per capita LAB consumption in 1991.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

LINEAR ALKYLBENZENE (LAB) MANUFACTURER 1.67

CONCLUSIONS

LAB continues to be the most cost-effective detergent intermediate, regardless of raw

material source. The continuing growth in LAB is spurred by increasing consumption in
countries outside the Organization of Economic Commercial Development (OECD).
Worldwide LAB consumption is expected to increase by some 650,000 MTA over the next
10 years. Increasing trade between various LAB-producing regions has led to more-uni-
form, high-quality requirements for the product in different parts of the world.
Developments in LAB technology have addressed the important issues confronting the
industry in the 1990s: improved yields and economics, product quality, and environmental
and safety considerations.
The use of large volumes of LAS derived from LAB over the last 40 years has result-
ed in extensive environmental studies of this surfactant by industry and consumer groups.
No other surfactant type has undergone such intense scrutiny. This scrutiny has resulted in
the development of improved methods for LAS detection outside of laboratory situations
and model predictions. The use of these techniques in real-world monitoring in various
countries during the last decade has only confirmed the long-term viability of LAS from
the standpoint of environmental safety.

ACKNOWLEDGMENTS

This chapter was adapted from a paper entitled “Growth and Developments in LAB
Technologies: Thirty Years of Innovation and More to Come,” by J. L. Berna and A.
Moreno of PETRESA, Spain, and A. Banerji, T. R. Fritsch, and B. V. Vora of UOP, Des
Plaines, Illinois, U.S.A. The paper was presented at the 1993 World Surfactant Congress
held in Montreux, Switzerland, on September 23, 1993.

REFERENCES

1. ARCO Technology Inc., Hydrocarbon Processing, 64 (11), 127, 1985.

2. J. F. Roth and A. R. Schaefer, U.S. Patent 3,356,757 (to Monsanto).
3. R. E. Berg and B. V. Vora, Encyclopedia of Chemical Processing and Design, vol. 15, Marcel
Dekker, New York, 1982, pp. 266–284.
4. E. Matthijs and H. de Henau, “Determination of LAS,” Tenside Surfactant Detergents, 24,
193–199, 1987.
5. J. L. Berna et al., “The Fate of LAS in the Environment,” Tenside Surfactant Detergents, 26, (2),
101–107, 1989.
6. H. A. Painter et al., “The Behaviour of LAS in Sewage Treatment Plants,” Tenside Surfactant
Detergents, 26, (2), 108–115, 1989.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 LINEAR ALKYLBENZENE (LAB) MANUFACTURE

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.