linear alkylate sulfonates.pdf

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February 1996 Surface-ActivePage 1583.9000 A

© 1998 by the Chemical Economics Handbook—SRI International

CEH Marketing Research Report

LINEAR ALKYLATE SULFONATES

ByRobert F. Modler

withRene Willhalm and Yuka Yoshida

CEH Marketing Research Reports provide comprehensive analysis, historical data and

forecasts pertaining to the international competitive market environment for chemical

products. Detailed supply and demand data are developed for the United States,

Western Europe and Japan with the cooperation of chemical producers and consumersworldwide.

Updated information may be available from the following CEH Program services:

CEH Online—The full text retrieval and update database. Updated monthly.

CEH CD-ROM—The entire contents of the CEH on one CD-ROM and including CEH

Online updates. Issued quarterly.

Manual of Current Indicators (MCI)—Updates of statistical data derived from

published sources. Issued quarterly.

The Economic Environment of the Chemical Industry (EECI)—Economic

indicators that impact the chemical industry; issued quarterly with the MCI.

CEH Inquiry Service—SRI Consulting researchers are available to answer your

questions.

U.S.A.—Telephone: 650/859-3900 Fax: 650/859-2182

Zurich—Telephone: 411/283-6333 Fax: 411/283-6320

Tokyo—Telephone: 813/3505-8916 Fax: 813/3505-8922


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 2583.9000 B


TABLE OF CONTENTS

Summary.................................................................................................................................................. 2

Manufacturing Processes......................................................................................................................... 5

Environmental Issues............................................................................................................................... 7

Supply and Demand by Region ............................................................................................................... 7United States........................................................................................................................................ 7

Producing Companies...................................................................................................................... 7Salient Statistics............................................................................................................................... 10Consumption.................................................................................................................................... 13

Household Products..................................................................................................................... 14Heavy-duty laundry detergents (powders and liquids)............................................................ 15Historical LAS consumption patterns...................................................................................... 17Light-duty liquid detergents..................................................................................................... 18

Miscellaneous household cleaners........................................................................................... 19Industrial, Institutional and Commercial Applications................................................................ 19Price................................................................................................................................................. 20Trade................................................................................................................................................ 22

Canada ................................................................................................................................................. 23Mexico ................................................................................................................................................. 23Western Europe.................................................................................................................................... 24

Producing Companies...................................................................................................................... 24Salient Statistics............................................................................................................................... 29Consumption.................................................................................................................................... 30

Household Products..................................................................................................................... 32Heavy-duty laundry powders................................................................................................... 32

Heavy-duty laundry liquids ..................................................................................................... 32Light-duty dishwashing liquids ............................................................................................... 32Other household cleaners......................................................................................................... 33

Industrial, Institutional and Commercial Applications................................................................ 33Price................................................................................................................................................. 33Trade................................................................................................................................................ 34

Eastern Europe..................................................................................................................................... 34Producing Companies...................................................................................................................... 34Consumption.................................................................................................................................... 37

Japan .................................................................................................................................................... 37Producing Companies...................................................................................................................... 37Salient Statistics............................................................................................................................... 39

Consumption.................................................................................................................................... 40Price................................................................................................................................................. 41Trade................................................................................................................................................ 41

Bibliography ............................................................................................................................................ 41


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SUMMARY

Linear alkylbenzene sulfonate (LAS) is the world’s largest-volume synthetic surfactant and is widely usedin household detergents as well as in numerous industrial applications. It was developed as abiodegradable replacement for nonlinear (i.e., branched) alkylbenzene sulfonate (BAS) and has largelyreplaced BAS in household detergents throughout the developed countries.

The products referred to as LAS or linear alkylate sulfonates include the various salts of sulfonatedalkylbenzenes as well as the free acid. LAS is generally produced in equipment that is also used toproduce other sulfonated/sulfated products; therefore, capacities far exceed demand for LAS alone.

The following table shows the 1994 supply/demand balance for LAS in the three major world areas:

Supply/Demand for LAS by Major Region—1994(millions of pounds)

UnitedStatesa

WesternEurope Japan Total

Capacityb 2,288 >2,866 364 >5,518

Production 610 968 333 1,911

Imports 5 neg 9 14

Exports 5 66 2 73

Consumption 610 902 340 1,852

(thousands of metric tons)

UnitedStatesa


Capacityb 1,038 >1,300 165 >2,503

Production 276.5 439 151 866.5

Imports 2 neg 4 6

Exports 2 30 1 33

Consumption 276.5 409 154 839.5

a. Production and consumption in Canada amounted to about 73 million

pounds (33 thousand metric tons), and production and consumption in

Mexico amounted to about 452 million pounds (205 thousand metric tons).

b. Capacity data for the United States and Western Europe refer to total

sulfonation capacity and include capacity to produce other sulfonated or

sulfated products; Japanese capacity data are for dedicated LAS production.

SOURCE: CEH estimates.

About 85% of LAS is used in household detergents, including laundry powders, laundry liquids,dishwashing liquids and other household cleaners. Industrial, institutional and commercial detergentsaccount for most of the other applications of LAS, but it is also used as an emulsifier (e.g., for agriculturalherbicides and in emulsion polymerization) and wetting agent. The following table shows a breakdown inthe use of LAS in the various end-use categories, as well as projections for future market changes over the1994-1999 period.


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Consumption of LAS by Major Region—1994(millions of pounds)

United States WesternEurope Japan Total

Laundry Powders 289 419 264.5 972.5

Laundry Liquids 148.5 97 9 254.5

Dishwashing Liquids 84.5 187.5 17.5 289.5

Other Household Cleaners 18.5 42 9 69.5

Nonhousehold Uses 69.5 156.

5

40 2

6

6

Total 610 902 340 1,852


UnitedStates


Laundry Powders 131 190 120 441Laundry Liquids 67.5 44 4 115.5

Dishwashing Liquids 38 85 8 131

Other Household Cleaners 8.5 19 4 31.5

Nonhousehold Uses 31.5 71 18 120.5

Total 276.5 409 154 839.5

Average Annual Growth Rate(percent)

1994-

1999 0% –2% –1.5%


LAS competes with several other major surfactants for use in household detergents. Some of thecompetitive surfactants have greater hard-water tolerance and better compatibility with enzymes, and aremilder than LAS. Because of its low cost and other favorable properties, however, LAS will remain amajor surfactant for many years. Although the consumption of LAS in the United States, Western Europeand Japan will probably remain unchanged or decline slightly, its consumption in the developing world islikely to grow rapidly.

Most of the LAS production is accounted for by detergent manufacturers that captively consume it. The

largest of these detergent manufacturers are the Procter & Gamble, Unilever, Colgate-Palmolive, Henkel,Lion and Kao groups. The latter two operate principally in Japan and other East Asian countries. Thebalance of LAS production is accounted for by chemical producers that also sell to detergentmanufacturers, either directly or through toll sulfonation arrangements. The large chemical producers of LAS also supply it to smaller detergent manufacturers that have no LAS production capability and toindustrial and institutional cleaning companies. The merchant suppliers may also sell LAS in the form of formulated products. Examples of large merchant suppliers are Stepan Company in the United States, theHuels Group in Western Europe and Tayca Corporation in Japan.


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MANUFACTURING PROCESSES

Linear alkylbenzene sulfonic acid is prepared commercially by sulfonating linear alkylbenzene (LAB)with either oleum (10-25% sulfur trioxide [SO3] in sulfuric acid) or an SO3-air mixture. In bothprocesses, sulfur trioxide is the sulfonating agent and the major product is p-alkylbenzene sulfonic acid.Both batch and continuous processes are used.

One advantage of the SO3-air route is that it is easier to produce lighter-colored sulfonic acid using thisprocess than with oleum. In addition, the oleum route leads to a product that contains a significant levelof by-product sodium sulfate. Although the oleum-derived product is readily formulated into powders, itis less desirable for use in formulating liquid products, where the excess sodium sulfate can createsolubility problems. Thus, the SO3-air process is the preferred route for LAS used in liquid formulations.Since merchant producers of LAS prefer a product that can be sold for either use, all have converted tothe SO3-air process. Also, merchant producers are able to use the same process and equipment to produceother sulfonates (e.g., alpha-olefin sulfonates and methyl ester sulfonates) and sulfates (e.g., alcoholsulfates and alcohol ether sulfates). Some detergent manufacturers that captively consume most of theirproduct in powders and liquids continue to use both routes, but they rely on the older oleum route for

most of their powder formulations and use the newer SO3-air route for most of the LAS used in liquidformulations. As of late 1995, only five oleum plants were operated by detergent manufacturers stillproducing LAS in the United States.

In a typical batch oleum sulfonation process, oleum is added to the LAB reaction mixture at the suctionside of a pump that is recycling the contents of the reactor. Under normal commercial conditions, 1.0-1.2pounds of oleum are required per pound of linear alkylbenzene. The reaction temperature is carefullycontrolled while the acid is added, and the reaction goes to completion during a 30- to 45-minutedigestion period. Excessive time or high temperature produces undesirable dark-colored products. In atypical continuous oleum sulfonation process, oleum and LAB are proportioned to a reactor mixing headand the reaction temperature is closely controlled using recycling of the reaction mixture through a heatexchanger. The reaction is generally completed in eight to fifteen minutes. Whether batch or continuous,

the reaction is carried out until sulfonation is 98-99% complete.

Sulfonation with oleum produces linear alkylbenzene sulfonic acid containing considerable excesssulfuric acid. If this material is neutralized with aqueous sodium hydroxide, the resulting low-activedetergent slurry contains about four parts of sodium sulfate for every six parts of the active LAS. Theselow-active detergent slurries are somewhat restricted in their areas of application because of the highsodium sulfate content. This shortcoming of the oleum-derived products may be partially overcome byadding enough water to the final sulfonation reaction mixture to dilute the sulfuric acid present fromabout 98% to 71-72%. At this concentration, the sulfuric acid is insoluble in the linear alkylbenzenesulfonic acid and separates as a second layer. Decanting of this sulfuric acid layer leaves an upper phasecontaining 87-90% linear alkylate sulfonic acid and only 7-9% sulfuric acid. When this product isneutralized with caustic soda, a high-active detergent slurry results.

In a typical batch SO3-air process, liquid sulfur trioxide is vaporized in a stream of dry air, and theresulting 5-15% SO3 stream is then reacted with the linear alkylbenzene.* As in oleum processes, goodmixing and heat removal are necessary to avoid oxidation and charring, which result in dark-coloredproducts. The reaction mixture is digested to complete the reaction. Air and the small remaining excess

* One variation of the batch process uses a liquid sulfur trioxide–sulfur dioxide mixture in which the sulfur

dioxide acts as a diluent for the sulfur trioxide, as a solvent for the reaction and as a refrigerant so that thereaction can be run at very low temperatures (–7 to –9°C).


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of sulfur trioxide (only a 3-5% molar excess is used) are removed. The reaction mixture is then hydratedwith a small amount of water to hydrolyze any alkylbenzene sulfonic acid anhydrides present in thereaction mixture. In continuous SO3-air processes, the color of the sulfonic acid products is improved bycareful control and maintenance of reaction temperatures. Variations in the method of temperature controlinclude recycling the reaction mixture through heat exchangers and the use of two or more reactorsconnected in series. When the mixture is neutralized with sodium hydroxide, a 96-97% sulfonate productis obtained.

The free acid in a liquid form (97% active) is the product most commonly sold in the merchant market,since it can be transported at the lowest cost. Shipping a 40% solution of the sodium salt is moreexpensive since it adds the cost of transporting large volumes of water. Most of the free acid is ultimatelyconverted to the sodium salt by detergent manufacturers and other end users. The sodium salt ispreferred, because it combines low cost with physical and performance properties suitable for a widerange of applications. For certain applications, however, other inorganic salts (e.g., ammonium, calcium,potassium) and organic amine salts (e.g., isopropylamine, triethanolamine) are also prepared.

It is estimated that an average of 0.707 pound of LAB is required per pound of sodium alkylbenzene

sulfonate produced. Production of linear alkylbenzene sulfonic acid and neutralization to thecorresponding sodium salt may be illustrated as follows:

mol wt:

+

R

246 (average C12 chain)

linear alkylbenzene

H2SO4 /SO3

oleum

or

SO3 /air


+ H2SO4

R

SO3H

linear alkylbenzene-

sulfonic acid

+ NaOH


R

+ H2O

SO3Na

sodium

alkylbenzene-


R

linear alkylbenzene-

sulfonic acid

SO3H

mol wt:


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ENVIRONMENTAL ISSUES

LAS has been safely consumed in large volumes throughout the developed world for over 25 years.*Although its use was once questioned in Western Europe because of its lack of biodegradability underanaerobic conditions, LAS is disposed of under aerobic conditions (i.e., sewage treatment plants), whereit does fully biodegrade. In any case, no legislation adversely affecting the use of LAS is expected inWestern Europe or elsewhere, and it is expected to remain the world’s largest surfactant used indetergents for many years.

According to a recent comprehensive risk assessment study carried out by the Netherlands government,the usage of LAS in laundry detergent powders does not involve any significant environmental risk.LAS, as well as other large-volume surfactants, are efficiently (over 99%) removed in the sewagetreatment systems. Similar conclusions were included in the end-of-year report of Britain’s Departmentof the Environment. This report states that LAS is “readily biodegradable” and its use in consumerproducts “poses no hazard to human health or the environment.”

The EU’s regulatory committee on ecolabeling recently approved detergents based on LAS, and they will

now qualify for the EU ecolabel.

SUPPLY AND DEMAND BY REGION

UNITED STATES

PRODUCING COMPANIES

The companies listed in the following table produce linear alkylbenzene sulfonic acid by sulfonation of alkylbenzene. Most of these sulfonators also neutralize at least a portion of their output to produce salts.

Only one of the domestic sulfonators—Vista Chemical Company—has captive supplies of linearalkylbenzene. In addition to the companies listed in the table, other companies produce salts frompurchased acids. According to industry sources, there are many such companies, and most use these saltscaptively.

A definitive identification of U.S. capacity dedicated to the sulfonation of linear alkylbenzene cannot bemade since chemicals other than linear alkylbenzene (e.g., alpha-olefins) can also be sulfonated in someof the same equipment. Also, facilities using SO3-air processes are often used for the sulfation of alcohols and alcohol ethoxylates. Therefore, the annual capacity figures given below represent onlypotential production capacity for LAS, provided that capacity was devoted solely to this task.

* Further information documenting biodegradation of LAS may be found in A. M. Nielsen et al., LAS

Biodegradation: Ultimate Fate of Alkyl and Ring Carbon, paper presented at the 1980 Annual Meeting of theSoap and Detergent Association, January 31-February 3, 1980, Boca Raton, Florida.


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>>U.S. Producers of LAS


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Gamble’s SO3-air plants at Baltimore, Maryland and Kansas City, Kansas, which do not produce LAS.


Since 1993, three producers have terminated production of LAS and other significant changes have

occurred. These are listed below.

BIT Manufacturing, Inc. began producing LAS at its plant, which previously produced onlybranched alkylbenzene sulfonates (BAS). Its production of LAS is believed to be very small.

Colgate-Palmolive shut down its Kansas City, Kansas and Jeffersonville, Indiana oleum and SO3-air units. However, the company added a new SO3-air unit at Cambridge, Ohio.

The Dial Corp. shut down its oleum unit at Bristol, Pennsylvania, but increased its SO 3-aircapacity at St. Louis, Missouri.

Kleenbrite Laboratories Inc. shut down its oleum sulfonation unit at Brockport, New York.

Pilot Chemical Company added a new 27-30 million pound-per-year SO3-air unit at Middletown,Ohio in 1993.

The Procter & Gamble Company closed its Quincy, Massachusetts and St. Bernard, Ohio oleumsulfonation units and consolidated production at the other three sites. Its SO3 units at Ivorydale,Ohio and Kansas City, Kansas continue to operate but have not produced LAS for many years.Instead, the plants produce alcohol ether sulfates; consequently, these plant sites have beendropped from the list.

Stepan Company increased its capacity for producing LAS from 900 million to 1,300 millionpounds per year.

Theochem Laboratories, Inc. shut down its oleum sulfonation unit at Atlanta, Georgia.

Safeway Stores, Incorporated closed its Oakland, California oleum unit.

Lever Brothers Company shut down its last oleum sulfonation unit at Los Angeles, California.

Of the eleven producers listed in the table, six are household detergent manufacturers that internallyconsume most or all of their LAS production for detergents. The other five sell nearly all of their LAS inthe merchant market, either as such or in surfactant blends. Four merchant producers that account for atleast 95% of the merchant market (including LAS-containing blends of surfactants sold to detergent

manufacturers) are Pilot Chemical Company, Stepan Company, Vista Chemical Company and WitcoCorporation. Of these four, Stepan is by far the largest, as shown in the following figure:


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U.S. Production of LAS by Manufacturer—1994

DetergentManufacturersfor Captive Use

(58%)

Stepan(26%)

Vista(8%)

Witco(4%)

Pilot(4%)

SALIENT STATISTICS

The following graph and table provide estimates of the U.S. supply/demand balance for LAS in recentyears.

>>U.S. Supply/Demand for LAS


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a. Exports are only for LAS as such; any LAS exported in detergent formulations is

not included.

b. About 90% of the LAS imports in 1985 were probably accounted for by LAS-

containing laundry detergent products imported from Canada. Imports in

subsequent years were of LAS itself.

c. Data includes United States and Canada.


The value of the 1994 U.S. production of LAS is estimated at $305-325 million.

Since 1966, the U.S. International Trade Commission (USITC) has reported data on the production andsales of alkylbenzene sulfonates. Data include linear alkylbenzene sulfonic acids and salts and branchedalkylbenzene sulfonic acids and salts (BAS). Production of the latter is estimated at 25-50 million poundsin recent years. However, an analysis of the data suggests that the total production reported by the USITC

is probably well below actual production levels. Some of the known producers are not cited by theUSITC as having reported production of LAS during recent years. In addition, the level of production of the LAS precursor, linear alkylbenzene (LAB), and the apparent consumption of LAS in household andindustrial detergents suggest that LAS production was considerably greater than reported by the USITC.For example, the 1990 production figure reported by the USITC was only about 662 million pounds forLAS and BAS combined, whereas the CEH estimate for that year is 906 million pounds for LAS alone.

The USITC data also provide a breakdown of U.S. production and sales of LAS and BAS by each salt,which may reflect the relative production and sales of these salts. The 1993 data reported by the USITCare listed in the following table:

Reported U.S. Production and Sales of Alkylbenzene Sulfonic Acid and Salts—1993a

(millions of pounds, 100% active basis)

Production Sales

Sodium Dodecylbenzenesulfonate 649.8 84.9

Dodecylbenzenesulfonic Acid 420.8 152.4

Triethanolamine Dodecylbenzenesulfonate 2.3 2.5

Calcium Dodecylbenzenesulfonate 5.1 8.2

a. Data are presented as reported in the source but are believed to be less than actual

production and sales levels. Also, dodecylbenzenesulfonic acid is all converted to its

salts, mainly sodium, so a great deal of double-counting is present in the data.

SOURCE: Synthetic Organic Chemicals, U.S. Production and Sales, U.S. International

Trade Commission.


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1

10

100

1,000

1975 1980 1985 1990 1995

U.S. Supply/Demand for LAS

Production

Imports

Exports

10

100

1000

Millions of Pounds Thousands of Metric Tons

Following the large-scale introduction of LAS in the mid-1960s, its production increased as it replacedthe slower-to-biodegrade BAS, and the use of light-duty liquid detergents using LAS grew rapidly.Production was relatively stable through the early 1970s, except for recessionary 1971 and 1975. During1976, production of LAS recovered, and it steadily increased through 1978 in response to the growingmarket for laundry liquids and nonphosphate laundry powders containing high LAS levels. Productiondeclined sharply in 1979-1982 as a result of several major laundry detergent reformulations in which LASlevels were greatly reduced. Production generally increased during 1983-1990 following the introductionof several household detergents with high LAS levels and strong growth in the household laundry liquidmarket. However, the production of LAS declined again in 1991-1994 as a result of many detergent

reformulations that reduced the LAS content of these products. Indeed, the 1994 LAS production levelwas the lowest since 1982. See the following section for a more detailed analysis of the issues thataccount for these reformulations and the fluctuating demand for LAS by the detergent industry over thelast two decades.


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CONSUMPTION

About 85-90% of the U.S. consumption of LAS is in household detergents, including laundry detergents(both powders and liquids), dishwashing detergents and various general-purpose household cleaners. Thebalance of the LAS consumption is in industrial, institutional and commercial cleaners, as well as in anumber of diverse industrial applications, where its use is not related to its cleaning properties.

The following table provides a breakdown of U.S. consumption of LAS by end use:

>>U.S. Consumption of LAS by End Use


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U.S. Consumption of LAS(millions of pounds)

1994 1999

Average AnnualGrowth Rate,

1994-1999(percent)

Household ProductsHeavy-Duty Laundry Powders 289 319 2

Heavy-Duty Laundry Liquids 148.5 121 –4

Light-Duty Liquids 84.5 80.5 –1

Miscellaneous Household Cleaners 18.5 19.5 1

Industrial, Institutional

and Commercial Applicationsa 69.5 73 1

Total 610 613 0%

a. Category may include some inventory adjustments by LAS producers.


The 1994 LAS consumption was 33% below the peak level in 1990. This drop largely reflectedreformulations that were unfavorable to LAS. The following sections present an analysis of each end-usearea.

Household Products

About 540 million pounds of LAS were consumed in U.S. household detergents in 1994, compared with820 million pounds in the peak year of 1990. From the late 1960s, when it replaced BAS, until 1993,LAS was the largest-volume surfactant consumed in household detergents. In 1994, however, alcoholether sulfates (AES) replaced LAS as the largest-volume anionic surfactants used in household detergents.The issues that led to this decline in LAS usage are described in considerable detail in the subsequentsections on the various household detergent types. Nevertheless, LAS remains a major surfactant inhousehold detergents.

Most synthetic detergent formulations are fairly complex mixtures, and manufacturers have developedconsiderable sophistication in varying the contents to achieve the desired performance at the lowestpossible cost. The choice of which surfactant to employ is based on the advertising claims themanufacturer wishes to make for a product and on cost/performance considerations that depend upon itsperformance in the formulated product and the ease of processing of the surfactant in combination withother ingredients in the formulation. The characteristics that have contributed to the widespread use of LAS include the following: excellent surfactant properties, low cost relative to alternative surfactants,

ease of processing into nonhydrous powders when spray-dried, favorable solubility characteristics for usein liquid formulations, compatibility with other surface-active agents used in mixed-actives systems,medium to high sudsing characteristics in formulations, and long-accepted biodegradability and favorableperformance under toxicological scrutiny.

The dominant U.S. producers of household detergents (and consequently the largest U.S. consumers of LAS) are The Procter & Gamble Company (P&G), Lever Brothers Company, Colgate-PalmoliveCompany, The Dial Corp. (producer of Purex® products), Huish Chemical Company, and Church &Dwight Co., Inc. (Arm & Hammer® products). Smaller household detergent producers using LAS


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include DeSoto, Inc.; Amway Corporation; Astor Products; the Consumer Products Division of DowChemical U.S.A.; Kleenbrite Laboratories Inc.; and USA Detergents, Incorporated.

The major manufacturers of household products produce and captively consume LAS, although some of these manufacturers also purchase additional quantities of LAS from merchant suppliers. The lattertransactions usually reflect the capacity limitations of some manufacturers for producing LAS using theSO3-air process, which is preferred for making LAS that is subsequently used in liquid products (see theMANUFACTURING PROCESSES section of this report). Many smaller detergent producers purchaseall of their LAS from merchant suppliers.

The major household product categories consuming large volumes of LAS are heavy-duty laundrypowders, heavy-duty laundry liquids and light-duty dishwashing liquids. (See the CEH Surfactants, Household Detergents and Their Raw Materials marketing research report for a discussion of theformulation of these products.) Smaller volumes of LAS are also consumed in a variety of general-purpose household cleaners.

The individual household detergent categories and their consumption of LAS are discussed in the

following sections.

Heavy-duty laundry detergents (powders and liquids)

U.S. consumption of LAS in household laundry detergents amounted to about 438 million pounds in1994. This represents a decline of almost 130 million pounds since 1993, all of which is accounted for bythe removal of LAS from the laundry liquids of P&G. This formulation change no doubt reflected anumber of considerations, one of which was a recognition of the tendency of high levels of LAS todeactivate enzymes in liquid systems. This and other issues are discussed later in this section. Futuregrowth for LAS depends upon both the growth and the composition (e.g., powders vs. liquids) of the U.S.laundry market and on the competition between LAS and other surfactants. The future design of new

energy-efficient washing machines will also have a big impact, but this will likely have no significanteffect until the year 2000.

The U.S. market includes both powder and liquid laundry products, with the liquids accounting for almost40% on a poundage basis. This contrasts sharply with other world areas, where liquids account for only avery small share. There has been very little growth in the U.S. consumption of laundry powders since1979; however, the volume of liquid laundry detergents consumed tripled between 1979 and 1988. Thisgrowth was greatly slowed by the introduction of compact laundry powders in 1991, but this may changeas the concentrated liquid laundry detergents, which were widely introduced in 1993, become morepopular. Furthermore, the U.S. Environmental Protection Agency (EPA) is considering new, lowerenergy consumption guidelines for future washing machines that are expected to reach the market in thenext century. Since these machines must use less hot water, most industry sources believe they will

probably require liquid detergents to effect a rapid and complete solution. The growing sales of laundryliquids were once a welcome development to LAB and LAS producers, since the surfactant levels,including those of LAS, were considerably higher in the liquids than in the powders. Overall surfactantlevels continue to be higher in liquids, but since the P&G reformulations previously mentioned, theaverage level of LAS is now lower in liquids than in powders. Thus, any future growth for liquids at theexpense of powders will no longer benefit LAS. Furthermore, the low-energy-consuming machines willalso require high agitation, which will require low-foaming surfactants. LAS is a high- to medium-foaming surfactant, and its use level might be limited in the new machines, although various defoamingingredients might be used to overcome this problem.


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The U.S. laundry market is expected to grow at an average annual rate of about 2.3% (washload basis)over the 1994-1999 period. During the 1980s, the overall growth in the U.S. market for laundrydetergents (powders and liquids) was much larger and greater than the estimates of many industrysources. The lower estimates were based largely on annual sales estimates provided by national surveysthat were in turn based on sales of detergents in supermarkets. These sales surveys often neglect theincreasing sales of laundry and other household products by mass merchandisers or “warehouse”consumer outlets. Since these outlets generally offer only a few brands at greatly reduced prices,detergent manufacturers must offer the lowest possible prices to secure shelf space at these outlets. Thisdevelopment has caused major restructuring in the detergent industry and intensified manufacturers’efforts to reduce formulation costs.

Thus, one of the most important considerations in the future consumption of LAS in home laundryproducts is the relative price for LAS compared with prices for the alcohol-based surfactants. LAS isderived from benzene and n-paraffins, both of which are in turn derived from petroleum. Petroleumprices declined significantly in 1986 and have remained relatively low since then, leading tocomparatively low and reasonably stable prices for benzene and n-paraffins. In contrast, the alcohol-based surfactants are produced largely from ethylene, which is derived mainly from natural gas liquids in

the United States. Prices for ethylene have been more volatile in recent years. Indeed, ethylene andethylene oxide prices increased sharply in 1987-1989, reflecting strong demand for ethylene in plasticsand other markets, along with a shortage in ethylene capacity. Prices for these products subsequentlydeclined in recessionary 1990-1992, but rose again in 1994 and 1995 as the U.S. economy grew strongly.Prices for ethylene declined somewhat in late 1995, but prices for ethylene oxide, which is used to makethe alcohol ethoxylates (AE) and alcohol ether sulfates (AES), are expected to remain strong for sometime. Although ethylene prices will continue to cycle in the future, both LAS and the alcohol-basedsurfactants are expected to remain highly competitive on a cost/performance basis for the foreseeablefuture.

On relative performance, AE has lower hard-water sensitivity than LAS, a consideration that is especiallyimportant in liquid laundry detergents, all of which lack an effective builder (i.e., a sequestrant for hard

water ions). However, LAS is more readily processed into powders than AE. LAS is generallyconsidered more effective than AE on heavy particulate soils (e.g., clays), whereas AE is more effectiveon body oil stains. Consequently, most manufacturers prefer to use a combination of both to obtain theoptimum performance for average washing conditions. Overall, these performance considerationssuggest that LAS will continue to be a cost-effective surfactant, especially in powders where itsprocessing characteristics are an advantage and where it has no adverse impact on enzyme stability.

LAS is also higher foaming than AE, which some consumers perceive as providing better cleaning.However, high foaming is a disadvantage in horizontal axis, rotating drum washers, where high foamlevels would result in overflow problems. This property could be a major disadvantage for LAS in thenew low-energy washing machines, which could use this design or another that will likely require highagitation. Some sources believe that defoamers can control this effect, but it is still likely to be a

disadvantage for LAS. The ultimate impact of this future development is uncertain, but it should not haveany significant impact until after the year 2000.

A third consideration in assessing the future growth of LAS is the degree to which enzymes are used inliquid detergents. Certain enzymes assist the action of surfactants by promoting the hydrolysis of proteinand starch stains. Others contribute to preserving the appearance of cotton fabrics after repeated washing.Some detergent manufacturers are not convinced that the high costs of enzymes are justified and believeconsumers are unaware of any improved performance they might contribute. However, the two largestdetergent manufacturers (P&G and Lever Bothers) do use them. Anionic surfactants in solution are


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 17583.9000 Q


known to inactivate enzymes over time, but the adverse impact of LAS is greater than with other anionics.As the level and complexity of the enzyme systems used has increased, this problem has become moreapparent. Although enzyme and LAB manufacturers have sought a solution, none is known at this time.P&G’s reformulation partly reflected this problem, but also the economic advantage of using its captiveproduction capability for methyl esters of fatty acids at its plant in Malaysia. These esters are a key rawmaterial for making the N-alkylglucosamide (AGA) and AES surfactants that replaced the LAS content of P&G’s liquid laundry detergents. There could be further large reductions in LAS if Lever Brothers alsoreduced the LAS level in its liquid products. However, Lever Brothers lacks the captive raw materialposition of P&G and would not have the same economic advantage in reformulating its liquids. Thus, allmanufacturers of liquid laundry detergents using LAS and enzymes must carefully balance the benefits of each and determine what their optimum levels are. Although LAS is vulnerable to replacement by othersurfactants in laundry liquids incorporating enzymes, a precipitous decline in LAS consumption in theseproducts seems unlikely.

A final consideration is the threat to LAS posed by environmental concerns, including concerns about thetetralin content of the raw material, LAB; the nonbiodegradability of LAS under anaerobic conditions;and its derivation from nonnatural (i.e., petroleum) sources, which are not renewable. LAB

manufacturers have already reduced the tetralin content of LAB to 1% or less in nearly all of the productsold to the major manufacturers and have provided evidence of the rapid biodegradability of the tetralinsthat remain. Although LAS is not biodegradable under anaerobic conditions, this is also true of severalother surfactants commonly used, as well as many other chemicals. Furthermore, only a small percentageof the LAS in the environment is finally destined for anaerobic conditions; LAS is largely disposed of insewage treatment plants under aerobic conditions. Most sources agree that the large-scale use of LAS forover 25 years without any observed problem is the best evidence of its apparent safety.

The issue of the preferability of “natural” and renewable raw material sources has been extensivelydebated. It is widely recognized that even surfactants based on natural (i.e., vegetable) sources requiresubsequent chemical processing that blurs any distinction between “natural” and “synthetic” products.Indeed, one life-cycle analysis study showed that the manufacture of a naturally derived surfactant (an

alpha-sulfo methyl coconut fatty acid ester) had a more adverse impact on the environment than theproduction of LAS. Unless future studies produce different results, this issue has only an emotionalappeal, rather than one that is based on strong environmental evidence.

The use of LAS in laundry powders should increase with market growth of the product over the 1994-1999 period. The consumption of LAS in liquid laundry products will decrease somewhat over the sameperiod as a result of the enzyme compatibility problems previously described. Overall, LAS consumptionin laundry detergents will be flat over the 1994-1999 period.

Historical LAS consumption patterns

Historically, the U.S. consumption of LAS in laundry detergents grew rapidly in the late 1960s, as itquickly replaced the less readily biodegradable BAS in these products. By 1969, this substitution wascomplete, and consumption of LAS grew more slowly, until it increased dramatically in the late 1970s asa result of two major developments. The first was the rapid growth in the use of laundry liquids (whichgenerally use higher surfactant levels than do powders). The second was the major reduction in thephosphate levels of detergents, which initially required higher surfactant levels to maintain acceptableperformance. The phosphate reduction reflected both the higher cost of phosphates and governmentrestrictions on their use in certain regions of the country. LAS was the surfactant of choice for most


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 18583.9000 R


producers in the late 1970s, and the volume of its consumption in laundry detergents reached a level of 519 million pounds in 1979.

When raw material costs began to rise as a result of the second world oil crisis in 1979, detergentmanufacturers began to reduce the cost of their detergent formulations by lowering the level of LAS andusing more of the alcohol-based surfactants. The price of ethylene (from which the alcohol-basedsurfactants are largely derived) had not risen as rapidly as n-paraffins and benzene (from which LAS isderived and which are tied directly to crude oil prices). As a result, the consumption of LAS in laundryproducts fell to only 365 million pounds in 1983 or 154 million pounds below the prior peak level in1979.

Consumption of LAS increased significantly in the mid-1980s as a result of lower crude oil prices and thesuccessful introduction of several new laundry products containing high levels of LAS, including P&G’sLiquid Tide® and Lever Brothers’ Surf ® laundry powder. Consumption continued to increase in the late1980s as a result of the growth in demand for laundry liquids and the subsequent introduction of compactlaundry powders that detergent manufacturers initially found easier to make from LAS than from othersurfactants. Thus, both production and consumption of LAS set new record levels in 1988 and again in

1990. Consumption declined during the 1991-1994 period as previously described.

Light-duty liquid detergents

Nearly 85 million pounds of LAS were consumed in light-duty liquid detergents in 1994. These productsare designed primarily for hand-washing of dinnerware and, to a far lesser extent, for hand-laundering of fine fabrics and hosiery. Most light-duty detergents use LAS in combination with lower levels of alcoholether sulfates (AES) and fatty alkanolamides (FAA). Alternatively, Procter & Gamble has consistentlyused higher levels of AES, in combination with other surfactants (e.g., alcohol sulfates, fatty amineoxides, amphoterics, and n-alkylglucosamides), and not used any LAS in its dishwashing liquids. Thisapproach may be too expensive for other producers, but Procter & Gamble has an economic advantage,

since it has a basic position in fatty amine oxides and also in detergent alcohols, from which AES isderived.

The sales of the light-duty liquids have shown very little growth over the last ten years. The main reasonhas been the increasing use of automatic dishwashers, which use a different type of detergent. Automaticdishwashing detergents are based largely on inorganic builders (e.g., phosphates and silicates) and useonly very low levels of specialty organic surfactants.

From 1982 through 1992, the consumption of LAS in light-duty detergents had been fairly stable.However, consumption fell sharply in 1993 and 1994, as several large manufacturers increased the use of milder surfactants, such as AES, alkylpolyglucosides (APG), and amphoterics, and lowered their LASlevels. As prices of some of these milder surfactants, especially AES, began to increase in 1994 and

1995, some detergent producers may switch back to LAS. However, Lever Brothers reportedly beganusing alpha-sulfo methyl esters in its dishwashing liquids, and this reformulation may further lower thelevels of LAS. Alcohol ethoxylates and alkylphenol ethoxylates cannot be employed in these products atsignificant levels because of the high level of skin irritation that would result from their use. Thus,detergent producers had fewer formulation options in hand-dishwashing liquids than in laundrydetergents. Until 1993, therefore, the consumption of LAS in this market tended to reflect the growth inthe overall use of dishwashing liquids and the market share of the light-duty detergents that use theLAS/AES/FAA formulation. This distribution had been more affected by the success of the advertisingpromotions of the major producers than by any raw material cost considerations.


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The greater emphasis on mildness that began in the 1990s led to the use of amphoterics and other mildcosurfactants, and this approach may become more common in the future as manufacturers seek topromote greater mildness as a product attribute. This trend will probably further reduce future LASconsumption in this market. However, LAS still has a significant cost advantage over most alternativesurfactants. Thus, the consumption of LAS in dishwashing liquids is likely to decline only slightly, at anaverage annual rate of –1% over the 1994-1999 period. This projection reflects the expectation of littlegrowth in the sales of the light-duty liquids and some product reformulations that are disadvantageous toLAS. The reformulations are likely to involve the greater use of milder surfactants in place of LAS.

Miscellaneous household cleaners

LAS is frequently present at low levels in numerous household cleaners. Inorganic salts and solvents areusually the major ingredients, and other surfactants are often used instead of LAS. Examples of theproduct categories and brand names that may contain LAS include floor cleaning powders (e.g., Spic andSpan®) and heavy-duty hard-surface cleansers (e.g., Mr. Clean®).

Small amounts of LAS may be used in several other household cleaning products. According to industrysources, specialty products such as some floor cleaners and laundry presoaks and prespotters annuallyconsume small amounts of LAS.

An estimated 18.5 million pounds of LAS were consumed in these products in 1994. There will probablybe a 1.5% average annual growth rate for these products and a 1.0% average annual growth in the LASconsumed in them for the 1994-1999 period.

Industrial, Institutional and Commercial Applications

In 1994, almost 70 million pounds of LAS were consumed in nonhousehold markets, mainly industrial,

institutional and commercial products and processes. This estimate reflects the difference betweenestimates of the total volume of LAS consumption and the volume consumed in household uses. As such,it can include some changes in customer inventories of LAS (both household and nonhousehold) and maybe subject to a much larger error than the other categories described. Thus, the reader should exercisesome caution in interpreting the significance of changes in the consumption estimates for this categoryover time.

Since nonhousehold markets for LAS are numerous and widely dispersed through industrial, institutionaland commercial establishments, they are difficult to quantify. This category includes nonhouseholdmarkets in which LAS is used in formulated cleaning products. Examples include commercial laundries,commercial and institutional restaurants using formulated hand-dishwashing liquids, janitorial cleanersused for offices and institutions, and transportation vehicle washing establishments. This category also

includes applications where the performance properties of LAS other than its basic detergency areimportant (e.g., emulsification of agricultural herbicides or of monomers in polymer processing).Although some developmental research on the use of LAS in tertiary oil recovery operations wasconducted (especially in 1981, when 3-5 million pounds were consumed in this use), it is unlikely thatany significant quantities of LAS have recently been or will be consumed in this application because of itshigher cost compared with that of petroleum sulfonates and the outlook for continued low crude oilprices.


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Other small or potential applications of LAS include sludge dispersion and its use in construction wall-board.

Growth in the consumption of LAS in all nonhousehold applications is expected to increase at an averageannual rate of 1% over the 1994-1999 period.

PRICE

Market prices for LAS have declined significantly during the 1991-1995 period. Average prices forlarge-volume purchases are well below list prices, and are probably in the $0.50-0.55 per-pound (100%active basis) range.

The following table presents typical list price histories for linear alkylbenzene sulfonic acids and salts:

>>U.S. List Prices for Linear AlkylbenzeneSulfonic Acid and Saltsa


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 21583.9000 U


1998e 86.5 83 72.5

a. Prices shown through 1971 and for 1977-1995 are list prices

on or about July 1 of the year indicated; data for 1973-1975

represent list prices as of December. The 1976 list prices

became effective October 1, 1976.

b. 96-97% active basis.

c. 100% active basis.

d. 60% active basis.

e. 60% active basis.


Since 1966, the U.S. International Trade Commission has reported unit sales value data (i.e., averagesales value) for sodium, calcium and triethanolamine dodecylbenzene sulfonates. These values include

both the branched (BAS) and linear (LAS) products. Since 1971, linear alkylbenzene sulfonic acid andsalts are estimated to have accounted for over 90% of the total volume of sulfonates used to calculatethese unit sales value data. The reported value of the sulfonic acid appears to be far below realisticaverages in recent years, and the reported value of the sodium salt appears to be much higher than likelyfor 1993. These data are listed in the following table:

U.S. Unit Sales Values for Alkylbenzene Sulfonatesa

(cents per pound)

Dodecylbenzenesulfonates TotalAlkylbenzene

Acid Sodium Calcium Triethanolamine Sulfonatesb

1966 -- 14 38 25 16

1967 -- 16 38 27 17

1968 -- 17 30 26 17

1969 -- 19 34 25 20

1970 -- 13 37 21 14

1971 -- 16 42 21 17

1972 -- 17 43 22 19

1973 -- 16 46 -- 15

1974 -- 26 64 22 27

1975 -- 32 77 28 34

1976 -- 33 73 41 36

1977 30 31 74 40 36

1978 31 27 76 42 35

1979 37 32 86 45 42

1980 45 39 91 56 49

1981 46 50 91 60 53

1982 43 37 75 60 44

1983 44 47 99 57 48

1984 46 50 98 56 50


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U.S. Unit Sales Values for Alkylbenzene Sulfonatesa (continued)(cents per pound)

Dodecylbenzenesulfonates TotalAlkylbenzene

Acid Sodium Calcium Triethanolamine Sulfonatesb

1985 46 54 102 58 52

1986 46 67 94 58 56

1987 47 66 109 59 57

1988 49 65 125 55 57

1989 53 60 145 59 59

1990 35c 69 111 82 46

1991 36c 74c 142 80 46

1992 32c 69c 164 81 42

1993 28.5c 81c 181 64 na

a. Calculated from rounded figures on the basis of 100% organic surface-active

ingredient. However, the reported values may be inaccurate in many years, as they

often exceed the list prices for the same year as shown in the preceding table.

b. Includes alkylbenzene sulfonic acid, the three salts listed and all other salts.

c. Reported values are believed to be inaccurate.

SOURCE: Synthetic Organic Chemicals, U.S. Production and Sales, U.S.

International Trade Commission.

During the 1970s, price increases for LAS generally reflected higher raw material (i.e., LAB) prices dueto either the energy shocks (1974 and 1979) or increasing demand for both LAB and LAS (1976-1979).Actual market prices declined slightly in 1982-1983, reflecting stable or declining world oil prices andreduced demand for LAS. Market prices increased again in 1984 and throughout the late 1980s as

demand for LAS increased, but dropped sharply over the 1990-1995 period.

Most large-volume sales of LAS are as the sulfonic acid, large volumes of which are toll-manufactured bysulfonators. In these arrangements, the detergent customer acquires the LAB raw material and has itdelivered to the sulfonator’s plant for conversion to LAS.

TRADE

LAS is not a significant item of international trade. Most LAS produced in the United States is consumeddomestically, as are most of the finished detergent formulations. Imports of LAS are estimated to havebeen only about 5-10 million pounds annually in recent years. Imports arriving by ship amounted to less

than 5 million pounds in 1994.

Exports of all alkylbenzene sulfonic acids (linear and nonlinear) were reported under export code# 554.4000 (U.S. Exports, Schedule E, U.S. Department of Commerce, Bureau of the Census) until 1988.Exports by ship amounted to less than 6 million pounds in 1994, most of which was as the calcium salt,probably for lubricant applications. The 1994 data could also include some nonlinear alkylbenzenesulfonates. The data exclude rail or truck shipments to Canada or Mexico. U.S. exports to these otherNorth American countries is thought to be only a few million pounds.


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CANADA

The following table lists Canadian producers of linear alkylbenzene sulfonic acid by sulfonation of alkylbenzene:

Canadian Producers of LAS

Company andPlant Location

Annual Capacityas of September 1995a

(thousands of metric tons)Sulfonation

Process Products

Lever Brothers Limited

Toronto, Ontario 16 na Sodium salt

Procter & Gamble Inc.

Hamilton, Ontario 16 na Sodium salt

Stepan Canada Inc.

Longford Mills, Ontario 18 SO3-air Acid and sodium salt

Witco Canada Inc.

Oakville, Ontario 13 SO3-air Acid and sodium salt

Total 63

a. Theoretical capacity, if production were solely devoted to 100% active linear alkylbenzene sulfonic acid.


Canadian production of LAS is estimated at about 33 thousand metric tons in 1994. Imports and exportsare thought to be relatively small. The great majority of LAS produced in Canada is consumed inhousehold laundry and dishwashing detergents in a manner similar to that described in the U.S. section of

this report.

MEXICO

The following table lists Mexican producers of linear alkylbenzene sulfonic acid by sulfonation of alkylbenzene:

Mexican Producers of LAS


Annual Capacityas of December 1995a


Process

La CaronaMexico, D.F. 32 SO3-air

Colgate-Palmolive S.A. de C.V.

Celaya, Guanajato 32 SO3-air

Nobleza

Mexico, D.F. na SO3-air


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 24583.9000 X


Mexican Producers of LAS (continued)




Process

Procter & Gamble de Mexico, S.A.

de C.V.

Celaya, Guanajato 136 SO3-air

Quimica Hoechst de Mexico, S.A.

de C.V.

Ecatepec, Mexico 4 SO3-air

Sanchez & Martin S.A.

Guadalajara, Jalisco na SO3-air

Sasil

Monterrey, Nuevo Leon 12 Oleum

Stepan Mexico S.A. de C.V. 6 SO3-air

Matamoros, Tamaulipas

Union Quimica

Mexico, D.F. na Oleum

Querataro, Guanajato 15 SO3-air

Total >237

a. Theoretical capacity, if production were solely devoted to 100% active linear

alkylbenzene sulfonic acid.


Mexican production and consumption of LAS is estimated at 205 thousand metric tons in 1994.

WESTERN EUROPE

PRODUCING COMPANIES

In Western Europe, the large multinational detergent manufacturers are the major producers of linearalkylbenzene sulfonic acid and its salts. They captively consume nearly all of the production of LAS informulated detergent products for household and industrial applications and use both oleum and the SO3-air processes. In addition, many other producers of LAS sell to the merchant market; however, some of these also consume part of their LAS production captively or for the production of formulated products.

Nearly all of the producers for the merchant market use the SO3-air process.

The following table lists the major Western European producers of LAS, with estimates of their sulfona-tion capacity. It does not list the individual capacities of all of the major detergent manufacturers, someof whose capacities are unknown. However, an estimate of the total sulfonation capacity of the unlisteddetergent manufacturers using SO3-air is included in the total under “Other.” The sulfonation capacitiesshown are not devoted solely to LAS, since the same facilities are often used for production of alcoholsulfates and alcohol ether sulfates.


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 25583.9000 Y


Western European Producers of LAS




Austria

Henkel Austria Ges.mbH

Wien 10

Belgium

Hickson Manro S.A.

Ougree 25

Denmark

Aarhus Oliefabrik A/S

Aarhus 3

Unilever Danmark A/SGlostrup na

France

Albright & Wilson Saint-

Mihiel SA

Han sur Meuse 30

Chimiotechnic SA

Venissieux 20

Henkel France S.A.

Pontivy

Reims

}

25

Procter & Gamble France SA

Neuilly sur Seine na

SEPPIC

Castres 3

Societe des Produits Chimiques

du Sidobre-Sinnova S.A.

(100% owned by Henkel

France S.A.)

Meaux 20

Unilever France SAHouburdin 30

Witco S.A.

Saint Pierre les Elbeuf 25


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 26583.9000 Z


Western European Producers of LAS (continued)




Germany

Akzo Nobel Chemicals GmbH

Dueren 10

BASF Aktiengesellschaft

Ludwigshafen 15

Chemische Fabrik Chem-Y GmbH

(100% owned by Kao Corporation)

Emmerich 25

Deutsche Shell AG

Koeln-Godorf 20

Deutsche Unilever GmbHMannheim 20

Henkel KGaA

Duesseldorf 90

Hoechst Aktiengesellschaft

Burgkirchen 15

Huels Aktiengesellschaft

Marl 115

Witco Surfactants GmbH

(formerly known as Rewo

Chemische Werke GmbH)Steinau 5

Zschimmer & Schwarz GmbH

& Co., Chemische Fabriken

Lahnstein 4

Italy

Albright & Wilson Castiglione Srl

Castiglione delle Stiviere 40

Albright & Wilson Patrica Srl

Patrica 30

Annunziata SpA

Ceccano 20

Auschem SpA

Seriate na

D.A.C. Industrie Chimiche SpA

Terranova dei Passerini 40


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 27583.9001 A






Italy (continued)

Henkel S.p.A.

Ferentino

Fino-Mornasco}

30

Lamberti SpA

Albizzate na

IBLA S.p.A.

Ragusa 18

Mirachem Srl

(formerly known as Panigal

Saponerie Italiane SpA)

Calderara 15

Mira Lanza SpA

Calderara na

Procter & Gamble Italia S.p.A.

Pomezia 20

Unil-It SpA

(100% owned by Unilever NV

[Netherlands])

Casalpusterlengo 30

Zschimmer & Schwarz Italiana SpA

Tricerro 6

Netherlands

Servo Delden BV

(100% owned by Huels

Aktiengesellschaft [Germany])

Delden 5

Norway

Unger Fabrikker A.S

Fredrikstad 35

Portugal

Shell Portuguesa SA

(formerly Espequimica)

Lisboa 20


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 28583.9001 B






Spain

Henkel Iberica, SA

Montornes del Valles 15

Hoechst Iberica, S.A.

Vilaseca 8

Kao Corporation S.A.

Olesa de Montserrat 10

Lipoquimicas Reunidas, SA

Zaragoza 3

Marchon Espanola, SA

(division of Albright & Wilson)Alcover 20

Petroquimica Espanola, SA

San Roque 25

Pulcra, s.a.

(100% owned by Henkel

Iberica, SA)

Barcelona 15

United Kingdom

Akcros Chemicals

Eccles 10

Albright & Wilson Ltd.

Surfactants Business

Whitehaven 50

Hickson Manro Ltd.

Stalybridge 55

Unilever PLC

Port Sunlight 25

Witco Surfactants

(formerly known as Rewo

Chemicals Ltd.)Maryport 5

Otherb 240-340

Total >1,300-1,400

a. Theoretical capacity, if production were solely devoted to

100% active linear alkylbenzene sulfonic acid. Sulfonation

capacities are not devoted solely to LAS.


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 29583.9001 C


b. Smaller producers and detergent manufacturers are located in

most of the Western European countries listed above.


The following table summarizes the Western European LAS capacities of the major groups of chemicalproducers:

Western European Producers of LAS by Company Group

Company Group

Annual Capacityas of December 1995


Major Detergent Manufacturersa 220

Henkel Group 205

Albright & Wilson Group 170

Huels Group 120

Hickson Manro Group 80

Shell Group 40

Unger Fabrikker A/S 35

Witco Group 35

Hoechst Group 23

Other >372-472

Total >1,300-1,400

a. Includes the Procter & Gamble, Unilever and Colgate-Palmolive

groups; the Henkel Group is also a major manufacturer, but its

production capacity is shown separately.


The industry is likely to undergo some consolidation in the near future. Thus, some smaller and/or oldersulfonation capacities will probably be closed or change ownership. At present, there is adequate sulfona-tion/sulfation capacity in Western Europe to produce all of the products that require this process.

SALIENT STATISTICS

The Western European supply/demand balance for LAS in recent years is shown in the following table:


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 30583.9001 D


Western European Supply/Demand for LAS(thousands of metric tons)

Production Imports ExportsaApparent

Consumption

1981 487 neg 53 434

1982 460 neg 27 433

1983 460 neg 25 435

1984 465 neg 20 445

1985 466 neg 20 446

1986 463 neg 33 430

1987 485 neg 35 450

1988 495 neg 35 460

1989 528 neg 45 483

1990 510 neg 35 475

1991 502 neg 35 467

1992 488 neg 30 458

1993 458 neg 30 428

1994 439 neg 30 409

1995 433 neg 30 403

1999 396 neg 30 366

a. May include some LAS in formulated detergent products.


The data illustrate a relatively stable Western European production of LAS during the 1982-1986 period,increased production during 1987-1989, and then declining production over the 1990-1995 period. See

the CONSUMPTION section for a discussion of the trends in recent years.

The sodium salt of the sulfonic acid accounted for 95-96% of the total Western European consumption of LAS. The calcium salt, which is used as an emulsifier in pesticide formulations, accounted for most of the balance. All the other salts (e.g., triethanolamine, isopropanolamine) represent only a tiny percentageof total LAS consumption. The merchant market sales of the sodium salt of LAS as an intermediate aredeclining due to its replacement by the free acid, which is cheaper to transport and is ultimately convertedlargely to the sodium salt by detergent producers.

CONSUMPTION

LAS is still the largest-volume anionic surfactant (excluding natural soaps) used in Western Europe. Inthe 1980s, its consumption increased at a rate of only about 1% per year, with a peak in 1989 of 483thousand metric tons. Since then, consumption has declined continously due to the shift to fatty alcohol–based products, such as AS and AES. The following table presents Western European consumption of LAS by end use in recent years:


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February 1996 LINEAR ALKYLATE SULFONATES Surface-ActivePage 31583.9001 E


Western European Consumption of LAS by End Use(thousands of metric tons)

Heavy-DutyLaundryPowders

Heavy-DutyLaundryLiquids

Light-DutyDishwashing

Liquids

Industrial,Institutional and

CommercialApplicationsa Total

1982 252 1 107 73 4331983 249 1 110 75 435

1984 250 1 114 80 445

1985 249 1 118 78 446

1986 215 20 115 80 430

1987 206 37 120 87 450

1988 200 45 130 85 460

1989 198 68 130 87 483

1990 205 55 128 87 475

1991 210 50 115 92 467

1992 207 47 113 91 458

1993 190 45 103 90 428

1994 190 44 85 90 409

1995 187 43 82 91 403

1999 163 38 70 95 366

a. Includes other household cleaners and industrial, institutional and commercial uses of LAS.


The following table presents estimates of the 1991 and 1994 consumption of LAS by end use, theprojected consumption in 1999 and the average annual growth rates:

Western European Consumption of LAS(thousands of metric tons)

1991 1994 1999

Average AnnualGrowth Rate,

1994-1999(percent)

Heavy-Duty Laundry Powders 210 190 163 –3

Heavy-Duty Laundry Liquids 50 44 38 –3

Light-Duty Dishwashing Liquids 115 85 70 –4

Other Household Cleaners 20 19 20 1

Othera 72 71 75 1

Total 467 409 366 –2%

a. Includes all industrial, institutional and commercial uses of LAS.



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Household Products

Heavy-duty laundry powders

An estimated 3.2 million metric tons of household laundry powders (this estimate may include someindustrial and institutional heavy-duty laundry powders) were consumed in Western Europe in 1993.This estimate includes both compact (i.e., concentrated and “ultra”) powders and regular laundrypowders. The great majority of the regular powders are of the low-foam type that typically contain acombination of LAS, soap and alcohol ethoxylates. The total surfactant level is normally in the 11-15%range, and the average LAS level is 5% to 6%. Some compact powders may still contain an average LASlevel of 6-8%. However, several major brands, such as Henkel’s Persil Mega Pearls® and P&G’s Ariel®

Futur, are believed to contain virtually only alcohol sulfates (AS).

An estimated 190 thousand metric tons of LAS were consumed in laundry powders in Western Europe in1994. Future changes in the technology for making detergents (e.g., the greater use of extruders andagglomeration, instead of spray-dry towers) may favor the use of AS instead of LAS because of theformer’s better crystallization properties. Using a conservative forecast, LAS consumption in laundry

powders is expected to decline 3% per year from 1994 through 1999, reducing its consumption in theseproducts to 163 thousand metric tons.

Heavy-duty laundry liquids

Heavy-duty laundry liquids were first introduced on a commercial scale in Western Europe in the early1980s. Major products have now been established in most countries, and the total 1994 Western Euro-pean consumption of laundry liquids is estimated at 550 thousand metric tons. Overall, the liquidproducts probably account for 15-17% of the total Western European laundry detergent market. The 1994market shares of liquid products are estimated at 6% in Germany and 20% in the United Kingdom.Concentrated laundry liquids were introduced into the UK market in 1994.

Most of the nonconcentrated heavy-duty liquid detergents contain alcohol ethoxylates, LAS and soap at atotal surfactant level of 35-45% and an average LAS content of about 10-13%. Newer types of heavy-duty liquid detergents often contain little or no LAS. Thus, LAS consumption in this application isexpected to decrease from 44 thousand metric tons in 1994 to 38 thousand metric tons in 1999.

Light-duty dishwashing liquids

The Western European consumption of light-duty (dishwashing) liquids in 1993 is estimated at 1.1million metric tons. The market for these products grew rapidly during the 1970s and early 1980s.However, the market is now saturated in most of the major countries, and demand growth has slowed.

The composition of light-duty dishwashing liquids differs widely, with the surfactant content rangingfrom 10% to 40%, although most of the products have a 20-30% surfactant level. The principalsurfactants used in normal dishwashing liquids are LAS, AES and secondary alkane sulfonates (SAS orparaffin sulfonates). The 1994 Western European consumption of LAS in this application is estimated at85 thousand metric tons. In recent years, usage of AES and betaines has been increasing at the expense of LAS in dishwashing liquids, and this trend has reduced the consumption of LAS in this application. New,concentrated light-duty liquids (e.g., P&G’s Fairy® Ultra) were introduced, but many of these products


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contain little or no LAS. Thus, the overall consumption of LAS in this application is expected to declineat an average annual rate of 4% over the 1994-1999 period.

Other household cleaners

This category includes a large number of household products that differ widely in their formulations;some do not contain LAS, while others may use up to 5% LAS. Consequently, this area is difficult toassess in terms of the volume of LAS consumed. This category also includes the older dishwashingpowders that have largely been replaced by dishwashing liquids. In recent years, there has been goodgrowth in sales of some of the small-volume specialty cleaner products, including several typesemploying LAS. Nevertheless, only a very small growth of LAS consumption in this category is likely.

Industrial, Institutional and Commercial Applications

LAS is used in industrial cleaners (e.g., for metals and textiles), in emulsifiers (e.g., for agricultural

herbicides and in polymer processing) and as a wetting agent. It is also used in many products sold tocommercial laundries and hotels, as well as institutions (e.g., hospitals and schools), and these productsoften resemble the household formulations for laundry, dishwashing and general cleaning. However, theymay have been specifically formulated for large-scale use involving special equipment. Only slowgrowth is expected for LAS in these applications.

PRICE

Typical Western European prices for LAS (delivered) are listed below.

Western European Prices for LAS

DM perKilogram

Dollars perKilogram

Exchange Rate(DM per dollar)

1983 1.98 0.776 2.55

1984 2.06 0.723 2.85

1985 2.08 0.707 2.94

1986a 1.96 0.903 2.17

1989 1.60 0.851 1.88

1991 1.50 0.904 1.66

1992 1.50 0.962 1.56

1993 1.40 0.848 1.65

1994 1.60 0.988 1.62

1995 1.50 1.071 1.40

a. Price is based on the average for the first quarter only.

SOURCES: (A) CEH estimates (data for DM PER KILOGRAM).

(B) International Financial Statist ics, International

Monetary Fund (data for EXCHANGE RATES).


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TRADE

Western European imports of LAS are negligible. Exports amounted to 30-35 thousand metric tons peryear over the last few years. See the SALIENT STATISTICS section for recent Western European tradedata. Some increased exports to Eastern Europe are possible, but this will probably be only for an interimperiod until surfactant and detergent manufacturers establish production facilities in Eastern Europe.

EASTERN EUROPE

PRODUCING COMPANIES

The following table lists the Eastern European producers of linear/branched alkylbenzenes (LAB/BAB)and alkylbenzene sulfonates (LAS/BAS). The information presented may be incomplete and has not beenverified by the individual producers listed.

Eastern European Producers of Linear/Branched Alkylbenzenesand Alkylbenzene Sulfonates



Company andPlant Location LAB/BAB LAS/BAS Remarks

Bulgaria

Yambolen

Yambol 50 -- Benzene and n-paraffins, Pacol HF process via

internal olefins.

Verila Ltd.

Ravno Pole -- 12

Commonwealth of Independent Statesa

Kaprolactam State Enterprise

Dzerzhinsk, Russia -- 15 SO3-air process.

Chimprom Production

Association

Pervomaisk, Russia -- 6

Vinniza, Ukraine -- 24 Mainly captive use.

Kirishinefteorgsintez

Oil RefineryKirishi, Russia -- 30 LAS plant as project.

Kirishi, Russia 75 -- LAB plant under construction. Start-up planned

for 1996.

Sovhenk (Henkel Russia)

Khimvolokno Plant

Engels, Russia -- 9 Captive production.


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Eastern European Producers of Linear/Branched Alkylbenzenes (continued)and Alkylbenzene Sulfonates



Company and

Plant Location LAB/BAB LAS/BAS Remarks

Commonwealth of Independent Statesa(continued)

State-Owned Complexes

Angarsk, Russia -- 24

Gorlovka, Ukraine 10 12

Novomoskovsk, Ukraine -- 12 Major laundry detergent producer.

Shebekino, Russia -- 7

Sumgait, Azerbaijan 70 -- Benzene and kerosene.

Sumgait, Azerbaijan 75 -- Paraffins.

Tashkent, Uzbekistan -- 6 Operating status uncertain.

Volgodonsk, Russia -- 10 Joint venture with Albright & Wilson.

Czech Republic

Lybar vel Vetg

(former Spolek pro Chemickou

a Hutni Vyrobu a.s.

Usti nad Labem -- 6

Rakona (Procter & Gamble)

Rakovnik -- 7

Hungary

Caola Kozmetikai es

Haztartasvegyipari Rt.Zalaegerszeg -- 7

Poland

Cussons

Wroclaw -- 10

Henkel-Polska S.A.

d. Raciborskie Zaklady Chemii

Gospodarczej “Pollena”

Raciborz -- 10 The company is 100% owned by Henkel.

Lever Polska

Bydgoszcz -- 10

Pollena

Gdansk -- 3


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Eastern European Producers of Linear/Branched Alkylbenzenes (continued)and Alkylbenzene Sulfonates



Company and

Plant Location LAB/BAB LAS/BAS Remarks

Romania

Chimicomplex SA

Onesti 8 --

Dero SA

Ploiesti -- 4

Detergent Factory of Timisoara

Timisoara -- 3

State-Owned Complex

Borzesti 10 -- Raw material unknown. Rodleben process.

Slovakia

Petrochema s.p.

Banska Bystrica

Dubova

--

na

na

16

The company is 100% owned by the Slovak

Republican State.

Yugoslavia, Former

Chromos Kutrilin

Zagrabria -- 6

Ohis

Skopye (Macedonia) -- --

Prva Iskra

Baric (Serbia) 50 9

Baric (Serbia) -- 6 Operating status uncertain.

Saponia Kemijska Industrija

Osijek (Croatia) -- 18

Total 348 282

a. Includes also regions of the former USSR not belonging to the Commonwealth of Independent States.



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CONSUMPTION

The following table provides estimates of detergent production in the Eastern European countries. Theranges shown indicate the uncertainties in these estimates.

Eastern European Production of Detergents


1990 1994

Bulgaria 60-70 10-20

Commonwealth of Independent

States (former USSR) 1,300-1,500 400-700

Czechoslovakia 80-140 --

Czech Republic -- 90-100

Slovakia -- 20-30

Hungary 40-80 50-70

Poland 190-240 180-230

Romania 60-90 40-50

Yugoslavia (former) 260-340 200-250

Total 1,990-2,460 990-1,450


The countries in the table above consumed about 2.3 billion metric tons of detergents in 1990, andconsiderably less in the following years. The per-capita consumption of detergents in Eastern Europe as awhole is in the range of 3-7 kilograms, whereas the corresponding number for Western Europe is 7-12kilograms (compact and conventional). The production of detergents in Eastern Europe is estimated atbetween 990 and 1,450 thousand metric tons in 1994. Assuming an average LAS/BAS level of about 7-10%, this would have required about 70-140 thousand metric tons of LAS/BAS in 1994.

JAPAN

PRODUCING COMPANIES

The major producers of LAS in Japan are listed in the following table. The large producers all use thesulfur trioxide process for sulfonating linear alkylbenzene (LAB). The estimated capacities listed in thefirst column of the table are for LAS only and do not necessarily represent the total capacity forsulfonation and/or sulfation. The second capacity column provides an estimate of the total sulfonation/ sulfation capacity of the LAS producers listed.


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Major Japanese Producers of LAS

Annual Capacity as of November 1995(thousands of metric tons)


Dedicated toLAS Production

Total Sulfonation/ Sulfation Capacity

Dai-ichi Kogyo Seiyaku Co., Ltd.Kyoto, Kyoto Prefecture 10 13

Kao Corporation 70 140

Kawasaki, Kanagawa Prefecture

Kitakyushu, Fukuoka Prefecture

Sakata, Yamagata Prefecture

Wakayama, Wakayama Prefecture

Lion Corporation 30 130

Chemical Products Division

Ichihara, Chiba Prefecture

Kawasaki, Kanagawa Prefecture

Kitakyushu, Fukuoka Prefecture

Sakai, Osaka Prefecture

Nissan Chemical Industries, Ltd.a

Nagoya, Aichi Prefecture 10 10

Tayca Corporation 45b 65

Taisho-ku, Osaka Prefecture

Otherc neg 30

Total 165 388

a. Production consigned by Nalken Corporation, which is a joint venture (50:50)

between Kyowa Hakko Kogyo Co., Ltd. and Vista Chemical Company (United

States).

b. Includes capacity for the production of some branched a

linear alkylate sulfonates.pdf

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