PCT WORLD INTELLECTUAL PROPERTY ORGANIZATION ‘Gtemations Buea INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (St) International Patent Classification 6 = (11) International Publication Number: WO 97/14676 AL eee (43) International Publication Date: 24 April 197 (24.04.97) ne _ 7 R, [US/US], Apartment 109, 1720 Arbor Lane, Crest Hil (21) International Application Number: PCT/US96/16688 USS A (22 International Fling Date: 17 October 1996 (17.109) | 5 jeans SARUSSL Steven 1; McDonnell Boehen Mule & Berghoft, td, 7th oor, 300 South Wacker Drive, Chicago, (20) Priority Data: N. 6b606 (US), (081546,339 20 October 1995 (20.1095) US (81) Designated States: BR, CA. CN, MX, US, Eurasian patent (60) Parent Application or Grant (AM, AZ, BY. KG, KZ, MD, RU, 13, TM. (63) Related by Continuation us 081546,339 (CIP) Filed on 20 October 1995 (20.1095) | Published (7 Applicant (for all designated States except US): STEPAN ‘COMPANY (US/USI: 22 West Frontage Road, Northfield TL 60093 (US), | (72) Inventors; and (78) InventorvApplicants (for US only): TULLY. Paul. S. [USIUS}; 2326 W. Medill, Chicago, TL 60647 (US), NEPRAS, Marshall, J. (US/US). S10 3S2nd Avenue, Burlington, WI $3105 (US). BERNHARDT, Randal. 1 [USIUS}, 39771 N. Whitenburg Drive, Antioeh, IL 60002 (US). HARTLAGE. James, A. (US/US): 3927 Britany Drive, Nomhbrook, IL. 60062 (US). MOHRING, William, With international search report. ($4) Tite: } ($7) Abstract IMPROVED PROCESS FOR PREPARING LINEAR ALKYLBENZENE SULFONATES Disclosed are processes for preparing lineu alkylbenzene sulfonic ackls and their comtesponding salts comprising: (a) treating a linear alkylbenzene with a sulfonating agent, where the linear alkylbenzene is produced by 2 reaction between an olefin and benzene: and (b Contacting the sulfonation product of (a) with a minture of a protic reagent and hydrogen peroxide to result in a sulfonic acid peroxideFOR THE PURPOSES OF INFORMATION ONLY Codes used to identity States pany 10 the PCT on the front pages of pamphlets publishing international applications under the PCT. AU Ausra Bear Bulan Bets CG Conn CH Soman CX Chan CZ Coch Repbic EE Eons FR Fane United Kingsom Guess Japan Kenya Kyran Democic Peape's Republic ot Koren epic of Koes ene siaska aia Laxenboare Monaco Repu of Molson Maga Maura mw Mala Meco Norway Pome Poros! Sian Sings Soren Swaaland Tak “Tenia nd Tobago UnetstnWo 97/14676 PCT/US96/16648 IMPROVED PROCESS FOR PREPARING LINEAR ALKYLBENZENE SULFONATES BACKGROUND OF THE INVENTION Field of the Inven ° The present invention relates to linear alkylbenzene onic acid compositions and methods for preparing such compositions having low color. It also neutralized linear alkylbenzene sulfonic acid compo: linear alkylbenzene sulfonates and methods such compositions ha ption Known methods preparing lir acids involve alkylbenzene starting material to remediate shown Scheme I below Scheme I: The Sulfonation of Linear Alkylbenzene Sulfonating agent ee eee nee R ‘SO3H <)> ° ikylbenzene sulfonic bleached and/or neutralized. Convent onal methods for preparing the starting linea alkylbenzene material typically involve a alkylation of benzene with a chloroparaff olefin in the presence of a suitable catalys More specifically, traditional methods have typically involved the use of chloroparaffins to alkylate benzene in the prese!10 15 20 25 WO 97/14676 PCTIUS96/16648, an aluminum trichloride catalyst. | This methodology, in addition to producing the desired alkylbenzene product, yields a@ variety of byproducts. Among these byproducts are branched alkylbenzenes (also. — known = ass 2-phenyl _—isomers), dialkylbenzenes, diphenylalkanes, alkyl indanes, alkyl tetralines and alkylated poly-aromatics, such as naphthalene and anthracene derivatives. Also, trace amounts of organochlorides and aluminum trichloride catalyst residues may be present. Modern methods for preparing the starting linear alkylbenzene typically involve a Friedel-Crafts alkylation of benzene with an olefin or n-paraffin the presence of a suitable catalyst: modern methods omit the usage of chloroparaffins. More specifically, modern methods typically involve the use of n-paraffins or olefins to alkylate benzene in the presence of an aluminum chloride catalyst cr the use of n-paraffins or olefins to alkylate benzene the presence of a hydrogen fluoride (HF) cr other catalyst su solia zeolite-basea catalyst. These methodologies produce the desired alkylbenzene product in overall conversion with significantly less formation of the previously mentionea byproducts. Conventional sulfonation processes involve reaction of the linear alkylbenzene with a sulfating agent, e.g., $03, S02-S03, oleum, or H2S0g, etc., to produce the desired sulfonic acid. To achieve maximum conversion of the linear alkylbenzene starting material to the desired sulfonic acid, at least a 1:1 ratio of sulfonating agent to alkylbenzene is required. However, sulfonation of a linear alkylbenzene starting material10 20 25 Wo 97/14676 PCT/US96/16648 derived from benzene and chloroparaffins with such an amount of sulfonating agent typically yields linear alkylbenzene sulfonic acids products having high, unsuitable amounts of color, as compared to sulfonation of a linear alkylbenzene starting material derived from benzene and n-paraffins or olefins. To address these problems a variety of bleaching methods have been developed. These methods have typically involved contacting a linear alkylbenzene sulfonic acid product with a bleaching agent such as hydrogen peroxide or the like. Alkylbenzene sulfonic acids, derived from chloroparaffins and benzene, which have been treated with hydrogen peroxide, are describec Patent No. 2,806,055, U.S. Patent No. 2,827,484, U.S. Patent No. 2,858,276 and U Patent No. 3,997,575. @ reducing the color in a sulfonic acid product derived om @ linear alkylbenzene prepared from chioroparaffin scurces, sulfo acid products of yibencel ef sulfonating agenz than ratio of sulfonating agent to linear eikylbenzene) such n-reacted linear alkylbenzene remains to satisfy commercial demands has not been realized. Finally, significant color reduction in a sulfonic acid product derived from linear alkylbenzene source, in which the sulfonation reaction to produce such a sulfonic acid product is carried out at reaction rate of one and one-half to four times that taught in the art of sulfonation, has not been realized. In summary,10 20 25 wo 97714676 PCT/US96/16648, there exists a need for a method capable of providing very low colored sulfonic acid products high yields. When treating a linear alkylbenzene with a sulfonating agent according to traditional methods, a typical molar ratio of sulfonating agent to linear alkylbenzene is from about 1.00:1.00 to about 1.04:1.00. A more preferred range of sulfonating agent to linear alkylbenzene is from about 1.01:1.00 to 1.02:1.00, A slight excess of sulfonating agent is generally believed to be necessary to drive the reaction to completion, i.e. to obtain a high level of conversion of linear alkylbenzene to linear alkylbenzene sulfonic acid. Conventional methods for maximizing © conversicn of linear alkylbenzene to linear alkylbenzene sulfonic acid typically include: (1) increasing the molar ratio of sulfonating agent to linear alkylbenzene, (2) providing an aging step for the sulfonic acid product after tne sz reaction has taken place. facn to nave a deletericus effect cn the sulfi metnocs empioyed. Usually a combina employed. As the ratio of sulfonating reagent linear alkylbenzene increases, the o or of the sulfonic acid product increases. Aging of linear alkylbenzene sulfonic acid typically involves heating the acid to a temperature of about 40-60°C for a period of time of abo 2-20 minutes. As the aging process at any elevated temperature for any reasonable period of time is employed, the color of the sulfonic acid product increases.10 2¢ ‘Wo 97114676 PCTIUS96/16648 SUMMARY OF THE INVENTION Processes for preparing linear alkylbenzene have been developed that avoid the use of chloroparaffins, but instead use olefins or n-paraffins as the source of the alkyl group. Such processes involve Friedel-Crafts alkylation of benzene with an olefin in the presence of a suitable HF or solid catalyst. These processes produce alkylbenzene having greatly decreased amounts of undesirable byproducts. It has been surprisingly discovered that sulfonation of alkylbenzenes produced by a reaction between an olefin or n- paraffin and benzene followed by subsequent treatment with protic reagent and hydrogen peroxide produces Linear alkylbenzene sulfo: acids having greatly decreased coll i.e., the amount of color reduction is substal al, with formation colorless sulfonic acids in some cases. Accordingly, the invention provides processes for preparing linear alkylbenzene paste che sorprises agent yield a sulfonation proa 1s produced by a reaction tetween an pare and benzene. The resulting linear alkylbenzene sulfonic acid is contacted with a protic reagent and hydrogen peroxide. The contacting is typically for a time and temperature sufficient to produce a linear alkylbenzene sulfonic acid having a greatiy reduced color. Sulfonation produ prepared according the inventive method typically have Klett colors less than 15. In certain embodiments of the inventive method, the sulfonation products have Klett colors less than about 2.10 20 Wo 97/14676 PCT/US96/16648, The invention further provides sulfonation products that are neutralized to provide a salt of the sulfonic acid (i.e. a sulfonate). it has been discovered that neutralizing 2 sulfonic acid product previously bleached with hydrogen peroxide provides an Unexpected amount of Klett color reduction to the al sulfonate product. Thus, the invention also encompasses a process for reducing the Klett color in a linear alkylbenzene sulfonic acid product that has previously been treated with a protic reagent and hydrogen peroxide, the process comprising contacting a s\ lfonic acid product with a neutralizing agent. Further, the invention encompasses a process for reducing the Klett color in a linear alkylbenzene sulfonate product t has previously been treated with a protic reagent, aydrogen peroxide, and a neutralizing agent, the process mprising contacting a sulfonate product with a reducing agent, such as sodium hypochlorite, to produce a s: unexpected amount of Klett color reaucticn. The inventio: further proviaes fonic acid compositions comprising from ap ercens 82 percent by weight linear alkylbenzene sulfonic acid anc about 0.5 percent to 15 percent by weight water. Water is present in such compositions to destroy undesirable sulfonic acid anhydrides which are formed during the sulfonation Process, Water is also present in such compositions to provide color stability to the sulfonic acid products. The invention further provides linear alkylbenzene sulfonic acid compositions comprising from about 8§ percent to 99 percent by weight linear alkylbenzene sulfonic acid an a10 as 20 25 wo 97/14676 PCTIUS96/1648 about 0.5 percent to 15 percent by weight water and preferably about 0.01 to about 0.5 percent by weight un-reacted linear alkylbenzene. In a more preferred embodiment, the invention further provides linear alkylbenzene sulfonic acid compositions comprising from about @5 percent to 99 percent by weight linear alkylbenzene sulfonic acid and about 0. percent to 15 percent by weight water and preferably about 0.01 to about 0.2 percent by weight un-reacted linear alkylbenzene. The invention further provides linear alkylbenzene sulfonic acid compositions prepared by rapid sulfonation conditions. When employing continuous falling film sulfonation, irrigation rates above 45 are considered rapid to one skilled the art. Standard irriga’ mn rates from about common for continuous falling film sulfonation. The standara de rigation rate /* } for falling wnere LAB linear alkylbenzene, P is 3.14, and D is the tube ameter of t @ falling fiim reactor. Irrigation rate is ndependent of tube length or the number of tubes in a reactor. The compositions sulfonated under rapid conditions comprise from about 85 percent to 99 percent by weight linear alkylbenzene sulfonic acid and about 0.5 percent to 15 percent by weight water and preferably about 0.01 to about 0.5 percent by weight un-reacted linear alkylbenzene.10 Wo 97714676 PCT/US96/16648 In @ more preferred embodiment, the invention further provides linear alkylbenzene sulfonic acid compositions prepared by rapid sulfonation conditions. These compositions comprise from about 85 percent to 99 percent by weight linear alk: benzene sulfonic acid and about 0.5 percent to 15 percent by weight water and preferably about 0.01 to about 0.2 percent by weight un-reacted linear alkylbenzene.10 25 WO 97/14676 PCT/US96/16648, DETAILED DESCRIPTION OF THE INVENTION As used herein, ear alkylbenzene (LAB) means an alkylbenzene having a straight or branched chain alkyl group of from about 8 to 22 carbon atoms. Linear alkylbenzene sulfonic acid or sulfonate (LAS) means an alkylbenzene sulfonic acid or sulfonate having a straight or branched chain alkyl group of from about @ to 22 carbon atoms. Klett color is defined by the equation (1000) (D)/2, where D is the optical density of the material being measured at 4 given concentration. The Klett color of the sulfonic acids and sulfonates described herein are measured at a 5 wei percent concentration in water. The present vention provides methods for preparing linear alkylbenzene sulfonic acid and salts of these acids. Surprisingly, the methods result linear alkylbenzene sulfonic acid and salt having substantially reduced amounts substantially sulfonated » ovides methoas ibenzene ads and onates at eased rates. Accordingly, the present invention encompasses processes for preparing linear alkylbenzene sulfonic acids (I) and linear alkylbenzene sulfonates (II) of the formulas a) -sou {som a (ay where R represents branched or straight chain alky) havi 8-22 carbon atoms; andwo 97/14676 PCT/US96/16648 represents an alkali metal, ammonium, or organic ammonium cation, or mixtures thereof. In general terms, the present invention is depicted in 5 Scheme II below: Scheme II Sulfonating Agent R H <)> SOs Protic Reagent’ Hydrogen Ko) Peroxide Neutralization R SO;H_ +—————_ R SO3H ("very light") is defined as m Light colored mat abou: ® © 8-22 carbon atoms.10 18 25 WO 97/14676 PCT/US96/16648 The starting linear alkylbenzene for use in this invention is preferably derived from the reaction of benzene and n- paraffins and/or olefins in the presence of a Friedel Crafts alkylation catalyst, such as hydrogen fluoride or aluminum chloride. Sulfonation In general, sulfonation of linear alkylbenzene starting material with @ sulfonating agent in accoraance with the principles of the invention is accomplished by treating the linear alkylbenzene starting material with 2 sulfonating agent. The sulfonating agent may be liquid or gaseous. Preferably, the starting linear alkylbenzene is in the 2 quid phase. treatment step typically occurs at a temperature from about 0°C to about 90°C and somewhat more preferably from about about Various sulfonating agents are fn. Representative £02-S03, #2804, sie in concentrated sulfur. lfur complexes, yi sulfonate-sulfur trioxide complexes and mixtures thereof. Sulfur trioxide (803) is a preferred sulfonating agent because of its vigorous reactivity. Sulfur trioxide also produces less byproducts than other sulfonating agents. It has been unexpectedly found that a linear alkylbenzene sulfonic acid, which is essentially free of un-reacted, i.e. un-sulfonated linear alkylbenzene, can be produced by employing a molar ratio of sulfonating agent to linear alkylbenzene of -11-10 15 2s Wo 97/14676 PCT/US96/16648, greater than about 1.04:1.00, in combination with an aging step an elevated temperature. It has been also found than a linear alkylbenzene sulfonic acid which is essentially free of un-reacted linear alkylbenzene can be produced by employing a molar ratio of sulfonating agent to linear alkylbenzene of about 1, without the need of an aging step. Typically, a sulfonation reaction is relatively fast and quite exothermic. Accordingly, care must be taken to avoid over-sulfonation in localized areas (i.e. charring) to adequately control the exotherm and to insure good contact between the reactants. Suitable methods of treating the ear alkylbenzene starting material with 8 sulfonating reagent include continuous agitation (batch sulfonation) methods, or by contacting @ gas stream containing the sulfonating agent against a moving surface film {continuous fa sulfonation) of linear alkylbenzene under turbulent whereby the various molecules are vigorous antermixed within the reaction mass. goth ba methods of sulfonation require that the exterior walls n vessel be cooled, for example, with a heat-exchange medium, providing a heat sink for the exothermic reaction conditions. When employing continuous sulfonation, a relatively rapid addition of sulfonating agent, for example, S03 in air, is desirable. One type of sulfonation which allows for such a rapid addition of sulfonating agent is falling film sulfonation. When practicing falling film sulfonation, $03 is normally introduced in a pressurized gas stream as a gas in 2 -12-10 15 20 25 WO 97/14676 PCTAISS6/16648 gas (i.e., S02, air, nitrogen or other relatively inert gas) in a so-called falling film reactor. Thus, in falling film sulfonation, the linear alkylbenzene is formed into a relatively thin film traveling down the interior walls of a tube reactor with the gas stream contacting thereon. Alternatively, a so-called wiped film reactor may be utilized so that a relatively thin film of linear alkylbenzene is contacted by the gas stream, mechanically wiped from the reactor walls at the area of contact and re-depos. downstream on freshly cooled reactor walls. When employing continuous falling film sulfonation of linear alkylbenzene under turbulent conditions, the color quality and composition of the linear alkylbenzene sulfonic acid product is effected by the rate of sulfonation and the control of the resulting exotherm, i.e. the efficiency of the heat sink provided. Irrigation rates from abo: common. When irrigation rates above + quality of the linear normally is degraded, as it is necessary heat sink to counter a: the reaction at such high irrigation rates ac = 3 i rigation rates is not typically practiced since such irrigation rates produce linear alkylbenzene sulfonic acid with unacceptable color. However, the need for an aging step can be omitted at high irrigation rates because the extreme exotherm in the reactor provides the necessary temperature for a sufficient period of time to maximize the conversion of Linear alkylbenzene to linear alkylbenzene sulfonic acid.210 15 25 wo 97114676 PCT/US96/16648 it has been found than iinear alkylbenzene sulfonic acids can be produced by employing irrigation rates of 45-100; irrigation rates of greater than 100 are also possible. It has also been found than a linear alkylbenzene sulfonic acid, which is essentially free of un-reacted, i.e., un-sulfonated linear alkylbenzene can be produced by employing a molar ratio of sulfonating agent to linear alkylbenzene, of greater than 1.04:1.00, in combination with the high irrigation rates described above. An aging step for this process is often not required. In batch mode sulfonation embodiments, 4 solvent may optionally be present during the treating step to both reduce the viscosity of the reaction mixture and another heat sink for the reaction. Presently, preferred solvents are sulfur dioxide, dioxane, dimethyl formamide, Cq to C20 hydrocarbons, nitroparaffins, acetonitrile, chleroalkyis, carboxylic acids, straight or branched aikylary nate pounds, having umene, yiene, olefins, paraffins, ana mx y any particular theory, tne reduce the viscosity of the reactants/reaction proaue liquid under reaction conditions. Some solvents such as, for example, sulfur dioxide may be gaseous even relatively low temperature so that super-atmospheric pressure may be required to maintain such solvents in liquid form. Generally pressures of up to about 100 p.s.i. or more are utilized. when solvents are present during the treating step, the amount of solvent may be present from about 0.01 percent to about 1000 percent by weight, based on the weight of the linear alkylbenz: aia20 45 20 25 Wo 97/14676 PCT/US96/16648 somewhat more preferably, the amount of solvent may be present from about 10 percent to about 1000 percent by weight, on the same basis. A presently preferred solvent is sulfur dioxide, because it complexes with sulfonating agents, particularly $03. Because of the difficulty of working with liquid sulfur dioxide, it is preferred to minimize the amount of sulfur dioxide utilized for the sulfonation reaction and to recycle the same where practical. Further, certain embodiments of the invention, the treating step may occur in the presence of a sulfonatable agent capable of reacting and/or complexing with any free and/or complexed $03. Without being bound by any particular theory, these sulfonatable agents likewise may function as aids in contr ing the viscosity of the reactants/reaction products, and as heat sinks for the exotherm of the sulfonation reaction The sulfonation agents also tend to ation sf the ear 8 yirenzene the sulfonating agen: Presently preferred sulfonatasi reaction and/or complexing with any free and/or compiexed sulfonating agents are linear or branched alkylaryl compounds, toluene, cumene, xylene, olefins, unsaturated esters, ammonia, organic ammonia derivatives, water and mixtures thereof. In embodiments where such sulfonatable agents are present during the treating step, the amount of sulfonatable agent present (if any) during the treating step may range from about 0.01 percent to about 1000 percent by weight, based on the weight of the sulfonating agent utilized. In preferred embodiments, the -15-10 15 20 25 wo 97/14676 PCT/US96/16648, amount of sulfonatable agent present during the treating step may range from about 10 percent to about 100 percent by weight, on the same basis. Further, in more preferred embodiments of the invention, both a sulfonatable agent capable of reacting and/or complexing with any free and/or complexed sul onating agent, as well as the earlier described solvents may be present in equal or different amounts during the treating of linear alkylbenzene with @ sulfonating agent, the aging step, the bleaching step and the neutralization step. Further, during the practice of certain embodiments of the vention, matrix sulfonation may also be utilized. Matrix sulfonation involves pre-mixing of linear alkylbenzene and sulfonatable agent moderator prior to treating with the sulfonating agent and subsequently allowing the sulfonation to occur. Examples of sulfonatable agent moderators i clude, but Mo is A ted to, pyridine, dimethylformamide, and trimethylamine. Such = method moderates agen: the feedstocn son sulfonation : minimizes the production cf ungesires cyer: podies. ther, during sulfcnation of linear alkylbenzenes, oop sulfonation may be practiced. During loop sulfonation, the treating step is repeated a number of times, either in 3 continuous loop-type re-circulating system or in batch re- sulfonation whereby additional sulfonating agent is added to an initially sulfonated termediate reaction product. During sulfonation cf linear alkylbenzene with particular sulfonating agents, whether “neat” or in the presence of a solvenz, diluent ~16-10 1s 2s ‘wo 97/14676 PCT/US96/16648 or other material, the reaction is conducted under sulfonation conditions, especially as described above. In general, after the sulfonation step (and the aging step if desired), linear alkylbenzene sulfonic acids are stabilized with water. The amount of water used is typically about 0.5 to 1.0 percent by weight, based on the weight of the linear alkylbenzene sulfonic acid. The water breaks up undesirable linear alkylbenzene sulfonic anhydrides which may be ‘ormed during the sulfonation step. Bleaching in general, after the sulfonation step, the resulting dark colored linear alkylbenzene sulfonic acid is contacted with a protic reagent and an oxidizing agent, e. hydrogen peroxide, where the contacting is performed at @ sufficient temperature produce a linear alkylbenzene ucea e bleach: ng before or after the water step. embodiments of the inventicn, the linear alkylbenzene sulfonic acid may be treated with an agent and a protic reagent in a batch mode, a continuous mode or a combination thereof. Further, in certain embodiments the invention, the linear alkylbenzene sulfonic acid may be treated with a premix of an oxidizing agent and a protic reagent in a batch mode, a continuous mode or a combination thereof. Representative protic reagents suitable for use in the bleaching step of the invention include, but are not Te10 1s 20 25 Wo 97/14676 PCT/US96/16648, to, water, alcohols of the formula R(OCH2CH2) ,0H where 1 to C29 and n is 0 to about 14, glycerin, ethanolamine, diethanolamine, and triethanolamine. In certain embodiments of the invention, the linear alkylbenzene sulfonic acid is treated with protic reagent in @ range of 0.50 percent to about 15.0 percent by weight, based on the weight of the linear alkylbenzene sulfonic acid. Somewhat more preferably, the amount of protic reagent used is 4 percent to 10 percent by weight, on the same basis. The most preferred oxidizing agent is hydrogen peroxide, which may be supplied in various and concentrations. The form of choice is a aqueous solution, with a concentration in the range of 0. percent to 70 percent, based on the total weight of the solution. A more preferred concentration is in the range of percent to 50 percent, on the same basis. In certain embodiments of the invention, the linear alkylbenzene sulfonic acid is treated with hydrogen peroxide in a range of 0 apout £.0 percent weight, pases on alkylbenzene sulfonic ac: ¢. Some what more amount cf nydrogen peroxide used is about pe: = by weight, on the same basis. batch mode of treatment, the linear alkylbenzene sulfonic acid and protic reagent are contacted at a te! perature of about O°C to about 80°C, for a time sufficient to produce a homogeneous mixture with agitation. In a more preferred mode of treatment, the linear alkylbenzene sulfonic acid and protic reagent are contacted at a temperature of about 25°C to about 50°C, for a time sufficient to produce a homogeneous mixture. The linear alkylbenzene sulfonic acid/protic reagent mixture is ~1e-10 15, 20 Wo 97/14676 PCT/US96/16648 then contacted with hydrogen peroxide at a temperature of about oC to about 80°C, for a time sufficient to produce a homogeneous mixture. In a more preferred embodiment, the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of about 8. In a most preferred embodiment, the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture w. agitation; said mixture posses a Klett color of less than about In a batch mode of treatment, the linear alkylbenzene sulfonic acid and a protic reagent/hydrogen peroxide pre- mixture solution are contacted at a temperature of about 0°C ¢ about 80°C, for a time sufficient =o produce s homogeneous mixture with agitation. In a stiii more grefe res moae eatment, the ear alkylbenzene sul reagent/hycrogen peroxide mixture are temperature of about 25°C to about 60°C, for a time sufficient produce a homogeneous mixture; said mixture posses a Klett color of less than about 8. In @ most preferred mode of treatment, the linear alkylbenzene sulfonic acid and protic reag nt/hydrogen peroxide mixture are contacted at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses Klett a color of less than about 2. To"10 20 25 ‘WO 97/14676 PCT/US96/16648, In @ continuous mode of treatment, the linear alkylbenzene sulfonic acid and protic reagent are contacted at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture. In a more preferred mode of treatment, the linear alkylbenzene sulfonic acid and protic reagent are contacted at a temperature of about 25°C to about 50°C, for a time sufficient to produce 2 homogeneous mixture. Without isolation, the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture. In @ sti. more preferred embodiment, the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient produce a homogeneous mixture; said mixture posses a Klett color of less than &. a most preferred embodiment, the linear alkylbenzene sulfonzs cid/protic reagent mixture is about 25°C Atacted with hyaroger, to about 60°C, produce 2 nomogenecus mixture; said mixture posses a Klett color less tnan about In a continuous mode o: eatment, the near alkylbenzene sulfonic acid and protic reagent/hydrogen peroxide pre-mixed solution are contacted at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture. In a still more preferred mode of treatment, the linear alkylbenzene sulfonic acid and protic reagent/hydrogen peroxide pre-mixed solution are contacted at a temperature of about 25°C to about 60°C, for a time sufficient 2 produce a homogeneous. -20-a5 20 25 wo 97714676 PCTIUS96/16648 In a still more preferred embodiment, the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of less than 8. In a most preferred embodiment, the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of less than about 2. The bleaching step of the invention has been found to significantly reduce the color of the starting linear kylbenzene sulfonic acids to a Klett of less than about 15, independent of the mode of sulfonation, the starting coler of sulfonic acid, the irrigation rate at which the sulfonic acid was produced (continuous falling mode), or the presence or absence of un-sulfonated linear alkylbenzene. Neutral on The light colored linear produced by the invention may be linear alkylbenzene sulfonates by a neutralization procedure. This neutralization procedure may take place immediately after the above described bleaching step(s) or at a later time. It has been discovered that neutralization of the bleached linear alkylbenzene sulfonic acid mixture to a pH of about 6.0 or to the greater affords an additional color reducing effe: final linear alkylbenzene sulfonate material, as compared to un-bleached linear alkylbenzene sulfonic acid. The color -21-10 1s 20 Wo 97/14676 PCT/US96/16648, reduction is typically about 5 to 20 Klett units. Without being bound by any particular theory, it is believed that this effect is an in situ activation of residual hydrogen peroxide. The above described neutralization can be effected utilizing a solution of base have a cation selected for the group consisting of alkali metals, ammonium cations, organic ammonium cations, and mixtures thereof. The neutrali 9 agent selected from, but not limited to, the group consisting of NaOH, MgO, Mg (OH) 2, KOH, Ca(OH) 2,._—s triethanolamine, diethanolamine, ammonia, isopropylamine, and mixtures thereof. All documents, e.g., patents and journal articles, cited above or below are hereby incorporated by reference in their entirety. In the following examples, all amounts are stated in percent by weight of active material uniess dicated otherwise. One skill doin the art will re may be made in the present invention spirit or scope of he invention. 7 rurther by the following examples wh as limiting the invention or scope of or compositions described herei: ae10 18 25 WO 97714676 PCT/US96/16648 EXAMPLE 1 Linear alkylbenzene sulfonic acid (LAS) is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene, with one of the following: Gaseous $03/air, 803/503, 42804 or ol: . Approximately 100g of LAS produced from the above reaction is heated to about 40°C for about 20 minutes (i.e., aged) to drive the reaction to completion. The LAS acid is then stabilized by the addition of about 0.5 wt. % water. The color of the crude sulfonic acid is deep red, with a Klett of about 40. The first step of the bleaching process involves combinii a 100g cf LAS with apout 6 g of water (6 wt. %} room temperature (23°C) with mixing, which produces @ 200°C exotherm. The temperature of the LAS/H20 slurry is adjusted to about 23°C and about 4g of H702 in the form of a 50% © aqueous solution (4 we. 4) is adde: The #20/H20: creates 4 hours oom temperat the sulfonic acid solut EXAMPLE 2 Linear alkylbenzene sulfonic acid (LAS) is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene, with one of the following: Gaseous S03/air, $02/S03, H2S0q or oleum. Approximately 100g cf LAS produced from the above reaction is heated to about 40°C for about 20 minutes are10 15 20 25 ‘wo 97714676 PCTUS96/16648 (i-e., aged) to drive the reaction to completion. The LAS acid is then stabilized by the addition of about 0.5 wt. § water. The color of the crude sulfonic acid is deep red, with a Klett of about 40. The first step of the bleaching process involves combining 100g of LAS with about 6 g of water (6 wt. §) at room temperature (23°C) with mixing, which produces a 20°C exotherm. The temperature of the LAS/H20 slurry is adjusted to about 38°C and about 4g of H202 in the form of a 50% active aqueous solution i4 wt. $) is added; this addition results in a 5°C exotherm. The H70/H702 treated LAS is allowed bleach approximately 45 minutes at a temperature of about 38°C. After this period of time the sulfonic acid solution had a Klett of about 2. EXAMPLE 3 Linear alkylbenzene sulfonic acid (LAS! :: greparea using sulfonation techniques ar alkylbenzene (LAB; produced by the one of the following: Gaseous oleum. Approximately 100g of LAS producea the reaction is heated to about 40°C for about 20 minutes aged) to drive the reaction to co pletion. The LAS acid is then stabilized by the addition of about 0.5 wr. % water The color of the crude sulfonic acid is deep red, with a Klett of about 40. The first step of the bleaching process involves combining 100g of LAS with about 6 g of methyl alcohol (6 wt. $) at room temperature (23°C) with mixing, which produces a 15°C exotherm. a‘wo 97/14676 PCTIUS96/16648 The temperature of the LAS/H20 slurry is adjusted to about 38°C and about 4g of H202 in the form of a 50% active aqueous solution (4 wt. %) is added; this addition results in a 5°C exotherm. The methyl alcohol/Hz02 treated LAS is allowed to bleach approximately 45 minutes at a temperature of about 38°C. After this period of time the sulfonic acid solution had a Klett of about EXAMPLE 4 Linear alkylbenzene sulfonic acid (LAS) is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB} produced by the reaction of an clefin and benzene, with one of the following: Gaseous $03/air, 502/803, H2S0q or oleum. Approximately 100g of LAS produced from the above reaction is heated to about 40°C for about (i.e., aged) to drive the reaction to completion. then stab. zed by the aadi The color of the cruge sult The first step of the bleaching process :avoives 100g cf LAS with about 6 g of water (6 wr. temperature (23°C) with mixing, which produces a 20°C exotherm The temperature of the LAS/H20 slurry is adjusted to about 38°C and about 2g of H202 in the form of a 50% active aqueous solution (2 wt. 8) is added; this addition results in a $°C exotherm. The H20/H202 treated LAS is allowed to bleach approximately 45 minutes at a temperature of about 38°C. After this period of time the sulfonic acid solution had a Klett of about 24, -25-10 1s 25 Wo 97/14676 PCT/US96/16648 Neutralization of the sulfonic acid solution is carried out at room temperature (23°C) by sequentially charging a vessel equipped with stirring means with: (1) a sufficient amount of H20/H202 treated LAS and water to prepare a slurry containing 35% by weight of neutralized LAS and (2) @ sufficient amount of caustic (NaOH) to neutralize about 75% of the acid in the slurry. This procedure results in a partially neutralized material having an initiai pH = 1 -2. The remaining caustic is then added slowly and the pH adjusted to approximately 8.5. | This method of neutralization avoids Foaming due to hydrogen peroxide destruction. After 24 hours at pH = 8.5 no active peroxide remains and the final 35% active slurry has a c r of Klett = 5. EXAMPLE 5 Linear alkylbenzene sulfonic acid (LAS) :s prepared using standard sulfonation techniques by kylbenzene LAB) procuced cy the reac penzene, with one of the following: Saseous or oieum. Approximately 100g ef LAS proauces above reaction is heated to about 40°C for about 20 minutes 2-€., aged) to drive the reaction to completion. The LAS acid then stabilized by the addition of about 0.5 wt. ? water. The color of the crude sulfonic acid is deep red, with a Klett of about $5. The first step of the bleaching process involves combining 100g of LAS with about 6 g of water (6 we. %) at room temperature (23°C) with mixing, which produces a 20°C exotherm. The temperature of the LAS/H20 slurry is adjusted to about 40°C -26-210 1s 20 25 Wo 97/14676 PCT/US96/16648 and about 1g of H202 in the form of a $0% active aqueous solution (1 wt. %) is added; this addition results in a 50°C exotherm. The H20/K202 treated LAS is allowed to bleach approximately 46 minutes at a temperature of about 40°C. After this period of time the sulfonic acid solution had a Klett of about 14. EXAMPLE 6 Linear alkylbenzene sulfonic acid (LAS) is prepared using standard sulfonation techniques at greatly increased irrigation rates by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene with gaseous S03 and air ine falling £ m reactor. The irrigation rate used is 76. The LAS product produced from the above reaction rates requires no digestion/aging. The resulting LAS acid is stabilized with 0.5 wt. % water. The color cf the crude sulfonic acid is black in ives combining wat mperature which proauces 18°C exotherm. The re of the LAS/H20 slurry is adjusted to about 35°C and about ig of H202 in the form of a 50% active aqueous solution lowt. $) is added; this addition results in a SCC exotherm. The H20/H202 treated LAS is allowed to bleach approximately 21 minutes at a temperature of about 35°C. After this period of time the sulfonic acid solution has a Klett of about 19. -27-10 20 25 WO 97/14676 PCT/US96/16648 ‘EXAMPLE 7 Linear alkylbenzene sulfonic acid (LAS) is prepared using standard sulfonation techniques at greatly increased i. igation rates by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene with gaseous S03 and air in a falling film reactor. The irrigation rate used is 76. The ratio of LAB:S03 is about 1:1.09. The LAS product produced from the above reaction rates requires no digestion/aging. The resulting LAS acid is stabilized with 0.8 wt. & water. The color of the crude sulfonic acid is black in appearance, with a Klett of about 109. The JHNMR and GC-MS an ysis indicates that the product contains no detectable residual LAB. The ‘St step of the bleaching process involves combining 100g of LAS with about 6 g of water (6 wr. & at a temperature ef about 35°C with mixing, which produces a 20°C exotherm. The temperature of the LAS/H20 slurry is adjusted to about 35°C and about 2g of H202 in the form cf a $0: active aqueous solution as addea ne 88C exctherm. eliowed zo bleacn approximatel temperatur. a Agte: this pericd of time the sulfonic acid solution has a Klett of about 24. EXAMPLE 8 Linear alkylbenzene sulfonic acid (LAS) is prepared using standard sulfonation techniques at greatly increased irrigation rates by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene with gaseous $03 and air in a falling film reactor. The irrigation rate used is 76. The ratio of LAB:S03 is about 1:1.09. The LAS product produced from -28-10 5 20 258 Wo 97/14676 PCT/US96/16648 the above reaction rates requires no digestion/aging. The resulting LAS acid stabilized with 0.5 wt. % water. The color of the crude sulfonic acid is black in appearance, with a Klett of about 109. The 1HNMR and GC-MS analysis indicates that the product contains no detectable residual LAB. The first step of the bleaching process involves combining 100g of LAS with about 6 g of water (6 wt. %) at a temperature of about 38°C with mixing, which produces a 20°C exotherm. The temperature of the LAS/H70 slurry is adjusted to about 35°C and about 2g of H202 in the form of a 50% active aqueous solution (2 wt. §) is added: The H20/H202 this addition results a 59°C exother: 20 treated LAS is allowed to bleach approximate minutes at a temperature of about 35°C. After this period of time the sulfonic acid solution has @ Klett of about 24. Neutra of the sulfonic acid solution is carried out at room temperature (23°C) by sequen vessel equipped with stirring means amou H20/H202 treated LAS and containing 35% by weight of sufficient amount of caustic (NaOH) te the acid in the slurry. This procedure results i neutralized material having an initial pH = 1 The remaining caustic is then added slowly and the pH adjusted to approximately §.5. This method of neutralization avoids foaming due to hydrogen peroxide destruction. After 2 hours at pH = 8.5 the final 35% active slurry has a Klett of about 5 Example 9