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 naturally occurring triglycerides from either vegetal or animal sources. The early alkylbenzene sulfonates (ABSs) were essentially sodium dodecylbenzene sulfonates (DDBSs), also known as branched alkylbenzene sulfonates (BABSs) obtained by the Friedel-Crafts alkylation of benzene with propylene tetramer, a mixture of branched C12 olefins. Dodecylbenzenes (DDBs) are then sulfonated with oleum or sulfur trioxide (SO3) and neutralized with sodium hydroxide or soda ash. Because of their lower cost and high effectiveness in a wide range of detergent formulations, DDBSs rapidly displaced natural soaps in household laundry and dishwashing applications. However, although excellent from a performance viewpoint, BABS exhibited 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.

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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 desorbents. Adsorptive separation techniques based on the molecular sieve action of 5- zeolites 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 UOPs Sorbex* simulated moving-bed technology; the UOP IsoSiv* process (formerly Union Carbides), which operates in the vapor phase also with a hydrocarbon desorbent; Exxons Ensorb process, which is also in the vapor phase but has an ammonia desorbent; or a similar technology developed in the former 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 UOPs Parex process for the selective recovery of high-purity pxylene 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 benzene 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 resulting olefins with benzene typically using hydrofluoric (HF) acid as catalyst. Shells 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, Hls AG in Germany. Alkylation of linear olefins with benzene also using an HF catalyst. The olefins are usually linear alpha-olefins (LAOs) from wax cracking (now discontinued), alpha-olefins from ethylene oligomerization, or linear internal olefins (LIOs) from olefin disproportionation. 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 nparaffins, followed by the alkylation of the olefins with benzene also using HF acid catalyst but without the separation and concentration of the LIO. UOPs Pacol* process for the catalytic dehydrogenation of n-paraffins and UOPs HF Detergent Alkylate* process for the alkylation of the LIO with benzene are prime examples of this approach. A similar approach is also practiced by Huntsman Corp. (formerly Monsantos).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.

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and higher-quality product. Although LAO and LIO obtained from sources other than dehydrogenation can equally be used, n-paraffin dehydrogenation routes have usually prevailed 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 catalyst, 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 UOPs dehydrogenation and alkylation technologies were in Japan and Spain at the end of 1968. Almost all the units built since then throughout the world employ UOP technology. Over the years, UOP has continued research and development and has introduced numerous improvements that resulted in improved economics 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 Chlorination and alkylation Dehydrogenation and alkylation High-purity olefins to alkylation Total Production, % 10 81 9 100

FIGURE 1.5.1 Routes to LAB.

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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 catalyst 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 quantities of neutralization products generated in the process. Hence, the advantages of a heterogeneous catalyst in this application have long been recognized. Aromatic alkylation has been demonstrated over many acidic solids, such as clay minerals, 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 development of a solid catalyst for the alkylation of benzene with linear olefins to produce LAB. The resulting Detal process was proved at UOPs pilot plants and at PETRESAs semiworks 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-catalyzed, fixed-bed alkylation unit. In the HF Detergent Alkylate process, olefin feed from the Pacol-DeFine units is combined 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-paraffins, 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 nparaffins 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 benzene 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 fractionation 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 associated 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 handled 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.

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LAB Recycle from Recycle Column Steam VE

HFS RR PC HS BC

RC

AR

AS

AM BAT Flush Linear Paraffin to Pacol Scrubbed Gas to Flare KR DD PN PSD Linear Detergent Alkylate Recycle Benzene KD Acid Relief and Vents Neutralized Heavy Alkylate Components SC KMT KD Knockout Drum SC Scrubber KMT KOH Mix Tank KR KOH Regenerator

LINEAR ALKYLBENZENE (LAB) MANUFACTURE

Linear Paraffin-Olefin Charge from Pacol Paraffin Dehydrogenation Unit

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Heavy Alkylate

FIGURE 1.5.2 HF Detergent Alkylate process.

ASD

ASD Acid Storage Drum AM Alkylation Mixer AS Alkylation Settler AR Acid Regenerator HFS HF Settler HS HF Stripper BC Benzene Column BAT Benzene Aluminum Treater

BS

PC RR RC VE BS PSD PN DD

Benzene Off-Spec Charge Paraffin Column Rerun Column Recycle Column Vacuum Ejector Benzene Stripper Polymer Surge Drum Polymer Neutralizer Degassing Drum

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Recycle Paraffins LAB Product Recycle Benzene Benzene Feed Olefin Feed Rx Vacuum

Benzene Column
FIGURE 1.5.3 Detal process flow scheme.

Recycle Paraffin Stripper

Paraffin Column

HAB Product LAB Colu

Research on the Detal catalyst showed that diolefins and some other impurities, mostly 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 aromatics 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 slightly 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-phenylalkane content of the LAB obtained in the Detal process. This higher content of 2-phenylalkane 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 sensitive to concentration compared with the HF derived product.

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LINEAR ALKYLBENZENE (LAB) MANUFACTURE

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FIGURE 1.5.4 Production of LAB from linear paraffins.

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TABLE 1.5.2

Comparison of HF and Detal LAB Typical HF LAB Typical Detal LAB 0.86 10 30 100 0.5 25 94 1030

Specific gravity Bromine index Saybolt color Water, ppm Tetralins, wt % 2-Phenyl-alkanes, wt % n-Alkylbenzene, wt % Klett color of 5% active LAS solution

0.86 15 30 100 1.0 1518 93 2040

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 estimated 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 openshop basis for a U.S. Gulf Coast location. The economic analysis is summarized in Table 1.5.3. The yields represent the production of LAB with an average molecular weight of 240. By-product credits include hydrogen at about 95 mol % purity, light ends, heavy alkylate, 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

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TABLE 1.5.3 Complex*

Economic Comparison of HF Detergent Alkylate and Detal Processes in a LAB HF Alkylation, per MT LAB Unit cost, $ Quantity 0.78 0.33 0.33 283 81 2.86 $ 350 99 20 21 14 2 25 545 24.4 70.1 2.2 Detal, per MT LAB Quantity 0.78 0.33 281 24 3.04 $ 352 100 21 28 14 1 27 548 24.2 56.6 1.9

Raw materials: n-Paraffins, MT Benzene, MT By-product credits, MT Catalysts and chemicals Utilities: Power, kWh Cooling water, m3 Fuel fired, million kcal Fixed costs Cash cost of production Cash flow, million $ (LAB at $850/ton) Estimated erected cost, million $ Simple payback, years (on fixed investment)

480 300 0.05 0.02 3.74

*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 Europe and former Soviet Union Africa Middle East Asia Americas Total
Note: MTA metric tons per annum.

1980 415 35 30 280 290 1050

2000 470 140 170 800 820 2400

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.
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North America 0.9-1.2 kg/yr Mideast 0.3-0.5 kg/yr North Africa 0.4-0.7 kg/yr India 0.2 kg/yr South Africa 0.1-0.3 kg/yr

Western Europe 0.8-1.4 kg/yr

Eastern Europe 0.3-0.4 kg/yr China 0.2 kg/yr

Far East 0.7-0.8 kg/yr

LINEAR ALKYLBENZENE (LAB) MANUFACTURE

Latin America 0.5-1.5 kg/yr

Southeast Asia 0.5-0.9 kg/yr

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FIGURE 1.5.6

Estimated per capita LAB consumption in 1991.

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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-uniform, 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 resulted 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. 266284. 4. E. Matthijs and H. de Henau, Determination of LAS, Tenside Surfactant Detergents, 24, 193199, 1987. 5. J. L. Berna et al., The Fate of LAS in the Environment, Tenside Surfactant Detergents, 26, (2), 101107, 1989. 6. H. A. Painter et al., The Behaviour of LAS in Sewage Treatment Plants, Tenside Surfactant Detergents, 26, (2), 108115, 1989.

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