MXPA00000837A - Improved processes for making alkylbenzenesulfonate surfactants and products thereof - Google Patents

Abstract

The present invention is in the field of processes for making alkylbenzenesulfonate surfactants. The processes herein include a combination of two essential steps, delinearization and alkylation. The delinearization step selected herein introduces particular types of limited branching into an aliphatic hydrocarbon having ten or more, but no more than about 16, carbon atoms. The hydrocarbon includes olefin having a hydrocarbon chain length suitable for detergent manufacture, e.g., C10-C14, or a corresponding paraffin. The second essential step is an alkylation step having an internal isomer selectivity of from 0 to no more than about 40 in which the hydrocarbon is used to monoalkylate benzene catalytically with an alkylation catalyst. Such alkylation catalysts preferably comprise an at least partially crystalline porous zeolite-containing solid, the zeolite having moderate acidity and intermediate pore size. Preferred alkylation catalysts include certain at least partially dealuminized acidic nonfluorinated mordenites. The processes herein further comprise sulfonating, neutralizing and incorporating the resulting modified alkylbenzenesulfonate surfactants into consumer products. The invention relates also to the products of the processes, including modified surfactants and consumer cleaning products containing them.

Description

IMPROVED PROCEDURE FOR MAKING SURFACTANTS OF ALKYLBENCENSULPHONATE AND PRODUCTS THEREOF FIELD OF THE INVENTION The present invention is in the field of processes for preparing surfactants based on alkylbenzenesulfonate. The methods of the present invention include a combination of two essential steps, de-linearization and alkylation. The de-linearization step selected herein introduces particular types of limited branching into an aliphatic hydrocarbon having ten or more, but not more than about 16, carbon atoms. The hydrocarbon includes olefin having a suitable hydrocarbon chain length to make detergents, for example from Cio-C, or a corresponding paraffin. The essential second step is an alkylation step having an internal selectivity to the isomer from 0 to not more than about 40, in which the hydrocarbon is used to catalytically monoalkyl the benzene with an alkylation catalyst. Such alkylation catalysts preferably comprise a solid containing partially crystalline porous zeolite, the zeolite having moderate acidity and intermediate pore size. Preferred alkylation catalysts include certain non-fluorinated, at least partially dealuminated, acidic mordenites. The processes herein further comprise sulfonating, neutralizing and incorporating the resulting modified alkylbenzene sulphonate based surfactants into consumer products. The invention also relates to the products of the processes, including modified surfactants and consumer cleansing products that contain them.

BACKGROUND OF THE INVENTION Previously, highly branched alkylbenzene sulfonate based surfactants, such as those having tetrapropylene base (known as "ABS" or "TPBS") in detergents, were used. However, it was found that they were poorly biodegradable. A long period followed by improved manufacturing processes for alkylbenzene sulfonates, making them as linear as practically possible ("LAS"). The overwhelming part of a large linear alkylbenzene sulfonate-based surfactant manufacturing technique is directed towards this goal. The commercially available large-scale alkylbenzene sulfonate processes in use in the United States today are directed to linear alkylbenzene sulphonates. However, linear alkylbenzenesulfonates are not without limitations; for example, these could be more desirable if they were improved in terms of their cleaning properties in hard water and / or cold water.

In the petroleum industry, various processes have recently been developed to produce, for example, low viscosity lubricating oil, of which the inventors have now discovered that they provide new perspectives on how to de-linearise hydrocarbons to a limited and controlled degree. However, such deliberate de-linearization is not a feature of any current commercial process in the field other than the manufacture of alkylbenzene sulfonate surfactants for consumer products. This is not surprising, in view of the overwhelming volume of the LAS-based surfactant technique focused on linear compounds and separated from the deslinealization. Most commercial processes for making alkylbenzenes are based on alkylation of benzene catalyzed by HF or aluminum chloride. Recently, it has been discovered that certain zeolite-based catalysts can be used to alkylate benzene with olefins. A process step as such has been described in the context of normally conventional processes for making linear alkylbenzene sulphonates. For example, the UTP DETAL® process utilizes a zeolite-based alkylation catalyst. It is believed that the DETAL® process and all other current commercial processes for making alkylbenzenesulfonate do not meet the requirements of internal selectivity towards the isomer of the process of the invention and of the alkylation catalyst defined hereinbefore. further, it is believed that the catalyst or catalysts of the DETAL® process lack the moderate acidity and the intermediate pore size of the alkylation catalyst used in the methods of the present invention. Other recent literature describes the use of mordenite as an alkylation catalyst, but such a description does not make the combination of specific process steps necessary for the present invention. Furthermore, in view of the desired linear character in the alkylbenzenesulfonate-based products of conventionally known processes, these generally also include steps directed toward the provision or processing of a substantially linear hydrocarbon, not a de-linearized one, prior to the alkylation. One possible exception is in the patent E.U.A. 5,026,933 which includes, for example, the oligomerization of lower olefins, such as propylene, under narrowly defined conditions using ZSM-23 deactivated with collidine to form a tetramer-containing composition that correctly has 1.3 methyl branches per chain, followed by fractionation and an alkylation using a mordenite-based catalyst. See example XVII. See also patent E.U.A. 4,990,718 in which an alkylbenzene is made by a process that produces a vinylidene olefin by dimerization in the presence of a chromium-based catalyst but in which the yield of vinylidene is adversely affected by the oligomerization and in which the distillation before alkylation. However, the procedures of the '933 and 718 patents have numerous limitations from the point of view of the detergent industry in terms of cost, limitations of the catalyst in the propylene oligomerization step or in the dimerization step of the olefin, the presence of large volumes of distillation fractions that would need to be discarded or find consumers who do not use detergents, and a limited range of product compositions, including mixtures of chain lengths that can be obtained. Such developments made by the petroleum industry are, in short, not optimal from the point of view of the expert formulator of detergent products.

TECHNICAL BACKGROUND The documents US 5,026,933; US 4,990,718; USA 4,301, 316; US 4,301, 317; US 4,855,527; US 4,870,038; US 2,477,382; EP 466,558, 1/15/92; EP 469,940, 2/5/92; FR 2,697,246, 4/29/94; USA 793,972, 1/7/81; US 2,564,072; USA 3,196,174; USA 3,238,249; US 3,355,484; USA 3,442,964; US 3,492,364; US 4,959,491; WO 88/07030, 9/25/90; US 4,962,256, US 5,196,624; USA 5,196,625; EP 364,012 B, 2/15/90; USA 3,312,745; USA 3,341, 614; US 3,442,965; USA 3,674,885; US 4,447,664; US 4,533,651; US 4,587,374; US 4,996,386; USA 5,210,060; US 5,510,306; WO 95/17961, 7/6/95; WO 95/18084; US 5,510,306; USA 5,087,788; 4,301, 316; 4,301, 317; 4,855,527; 4,870,038; 5,026,933; 5,625,105 and 4,973,788 are useful as background for the invention. The manufacture of alkylbenzenesulfonate based surfactants has recently been reviewed. See volume 56 in the series "Surfactant Science", Marcel Dekker, New York, 1996, including in particular chapter II entitled "Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108 which includes 297 literature references . The documents referred to in the present invention are incorporated in their entirety.

BRIEF DESCRIPTION OF THE INVENTION The present invention is predicated upon an unexpected discovery that combining a specifically defined step or steps to de-linearize a non-inferior olefin or paraffin ("non-inferior" meaning having 10 or more carbon atoms) with a particularly defined selective alkylation step gives as a result an unexpectedly superior alkylbenzene sulfonate surfactant product. Accordingly, in one aspect, the present invention relates to a process for preparing alkylbenzene sulfonate based surfactant which is suitable for use in cleaning products such as laundry detergents, hard surface cleaners, dishwashing detergents and detergents. similar, said method comprising a) reducing the linear character of an olefin, preferably one having a molecular weight of at least about 126 and not more than about 280, preferably not more than about 224, by an isomerization step of the base structure, in the presence of an isomerization catalyst restricted to the base structure, of a substantially linear olefin preformed to have at least said molecular weight; and b) a monoalkylation step having low internal selectivity towards the isomer (from 0 to no more than 40, preferably from 0 to no more than 20, more preferred from 0 to no more than 10 using measures defined later herein) , wherein the product of step (a) is reacted with an aromatic hydrocarbon which is selected from benzene, toluene and mixtures thereof in the presence of a particularly defined alkylation catalyst. Such a catalyst contains a medium pore zeolite of moderate acidity defined in detail hereinafter. A particularly preferred alkylation catalyst contains non-fluorinated, acidic, at least partially dealuminated mordenites. In another aspect, the invention relates to a process for preparing a modified alkylbenzenesulfonate-based surfactant which is suitable for use in cleaning products, said method comprising a) a step of arriving at (making or supplying) an alkylating agent of reduced linearity that is selected from an olefin having molecular weight, n, of at least about 126 and not more than about 280 and produced by a sequence of steps comprising: (i) shaping the base structure of a paraffin linear having molecular weight of n + 2 wherein n is said molecular weight of said olefin; and (i) dehydrogenating the isomerized paraffin; and b) a monoalkylation step in which the reduced linearity alkylating agent of step (a) is reacted (i.e., the hydrocarbon produced in that step) with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst identical to that used in the embodiment described in the preceding paragraph. The invention also encompasses a method of conforming to any of the above aspects or embodiments of the invention having the additional steps of c) sulfonating the product of step (b); and one or more steps that are selected from (d) neutralizing the product of step (c); and (e) mixing the product of step (c) or (d) with one or more adjunct materials for cleaning product; thus forming a cleaning product. In addition, the invention also encompasses cleaning products including heavy duty and light duty laundry detergents, hard surface cleaners, dishwashing detergents, soap bars, detergent tablets or detergent gels, shampoos and the like formed by any of the described procedures. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All the cited documents are, in a relevant part, incorporated in the present invention for reference.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a block diagram of a conventional commercial process for making linear alkylbenzene sulphonate based surfactants. Figures 2 to 4 are block diagrams of procedures according to the invention. Figure 5 is a block diagram of a literature procedure. Capital letters, for example A, B, C, are used to indicate steps in these procedures. Numbers such as 1, 2, 3 refer to the entry and / or exit of compositions from the steps of the procedure.

DETAILED DESCRIPTION OF THE INVENTION PROCEDURES WITH REGARD TO THE DRAWINGS The methods of the present invention will be better understood with reference to Figures 1 to 5. As indicated, Figure 1 is a block diagram of a conventional commercial process for manufacturing linear alkylbenzene sulfonate based surfactants. . Figures 2 to 4 are block diagrams of methods according to the invention. Figure 5 is a block diagram of a literature procedure.

For purposes of comparison with the process of the present invention, a conventional commercial process for making LAS, for example from kerosene or other paraffins, includes steps AE in Figure 1. Based on the conventional judgment that substantial linearity (usually> 90%, commonly> 95%) is essential, efforts are usually made to provide a linear supply material or increase the linearity of the supply material, for example using the UOP MOLEX® sieving procedure to eliminate the branched paraffins. In Figure 1 the input stream 1 is typically kerosene. The product of step A, ie 2 in Figure 1, is a linear or substantially linear paraffin, commonly a linear paraffin of C? O-C? 4. Step B, a dehydrogenation step, in commercial practice is commonly the UOP PACOL® process optionally supplemented by the UOP DEFINE® process (converting the DEFINE® process any of the dienes in the supply into monoolefins), and produces monoolefins linear or substantially linear as the product 3. Linear olefins are alkylated, typically using HF or aluminum chloride in step C, although more recently, improvements over the HF process take the form of liquid phase alkylation steps using a catalyst silica / fluorinated amorphous alumina base. Such procedures include the DETAL® procedure of UOP and CEPSA (Petresa) and the methods described in the U.S.A. such as E: U: A: 5,344,997, E: UA: 5,196,574 and E: U: A. 5,334,793. See also E: U: A: 5,245,094. The alkylbenzene products, 4, are sulfonized D and the alkylbenzenesulfonic acids produced, 5, are neutralized E. The sulfonation and neutralization steps can be carried out in a facility far from that used to produce the linear alkylbenzene (LAB) A-C. Referring to the procedure in Figure 2, it is required that the method of the present invention, surprisingly, have a reduction in linearity or a de-linearization step, in which the deslinealization is applied to an olefin supply material not lower or paraffin not lower, 6. This step is shown as step F in Figure 2 and is exemplified in Figures 3-4 by specific steps H and J to introduce limited branching in paraffin or non-inferior supply olefin (identified as 9 and 15 in figures 3-4). Further, it is required that the method of the invention have a step, shown as step G in Figures 2-4, of hydrocarbon alkylation (identified as 7.11, and 16 in Figures 2-4), with a catalyst of alkylation defined in detail later herein. Such catalyst in the present is generally by at least partially crystalline (not amorphous) and not based on HF or its derivatives (including silica / fluorinated alumina) or aluminum chlorides which are strongly acidic and / or give products normally not acceptable for compositions. The catalytic alkylation step herein may more particularly utilize a specifically selected zeolite described and illustrated hereinafter. Modified alkylbenzene (MAB) produced in the procedures shown in Figures 2-4 and shown as 8, 12, 13, 17 and 18, is sulfonated and neutralized by individually known steps shown as D and E. In the preferred methods, an additional step, (shown in Figures 3-4 as 14 and 19) is used to combine the Sulfonated MAB with detergent adjuncts to produce novel cleansing products for the consumer, shown in step I. Step B, a dehydrogenation step, in the procedure of Fig. 3 produces monoolefins of reduced linearity or de-linearized as product 10. procedures shown in the drawings, whether these are conventional and commercially practiced, for example figure 1, or known from the literature, for example, figure 5, or novel, for example figures 2-4, can include any steps additional not shown in the figures but known in the art. Such steps can be introduced between the steps shown in the figures. Such steps include, for example, passing an intermediate current through a sorption separation zone using non-acidic zeolites to limit the dialkyltetralins in the alkylation supply material. See, for example, patent E.U.A. 2,276,231. Other such steps include the common distillation steps of the alkylbenzenes. The procedure shown in figure 5 as indicated above reproduces a method known in the art, that of the patent E.U.A. 5,026,933, for comparison purposes. It is not known if the procedure of the patent E.U: A. 5,026,933 is in commercial use. The notable limitations of this procedure in addition to its presumed lack of successful commercial exploitation include that it is limited to lower olefin supply materials, shown as 21, specifically propylene and / or butylene (step K in Figure 5); fractionation is required, shown as 22, (step L in figure 5) and there are large proportions of rejected materials not useful for making surfactants for cleaning, shown as 20. Note that the oligomerization of propylene and / or butylene or other olefins " "lower" as defined herein is not practiced in the essential steps of the method of the present invention. The stream of non-rejected materials 23 is then reacted with an aromatic hydrocarbon in the presence of a restricted alkylation catalyst (step M in Figure 5) whereby a linear aromatic alkyl compound is produced, 24.

Procedures in greater detail As indicated in the brief description, the present invention relates to a process for preparing modified alkylbenzene sulfonate based surfactant suitable for use in cleaning products such as laundry detergents, hard surface cleaners, detergents for dishwashing and the like. The term "modified alkyl benzene sulfonate based surfactant (MAS)" refers to the product of the methods herein. The term "modified" as applied to either the novel alkyl benzene sulfonate or novel alkylbenzene (MAB) based surfactants is used as a qualifier to indicate that the product of the present process is of a composition different from that of the surfactants based on alkylbenzenesulfonates used until nowadays in commerce. More in particular, the compositions herein differ in terms of the composition of the so-called "ABS" or very low biodegradable alkylbenzene sulphonates, and of the so-called "LAS" or linear alkylbenzenesulfonate-based surfactants. Conventional LAS-based surfactants are currently commercially available through various processes including those based on the alkylation of benzene catalyzed with HF or aluminum chloride. Other LAS-based surfactants include LAS made by the DETAL® process. The modified alkylbenzene sulfonate based surfactants herein are also different in composition from those made by alkylation of linear olefins using fluorinated zeolite based catalyst systems, including fluorinated mordenites. Without being limited to the theory, it is believed that the modified alkylbenzenesulfonate-based surfactants herein are slightly uniquely branched. These typically contain a plurality of isomers and / or homologues. Frequently, this plurality of species (often tens or even hundreds) is accompanied by a relatively high total content of 2-phenyl isomers, the content of 2-phenyl isomer exceeding at least the current DETAL® process and commonly achieving more than 50% or even more than 70% or more. Furthermore, the modified alkylbenzene sulfonate-based products herein differ in the physical properties of the known alkylbenzene sulfonate based surfactants, for example by having an improved cleaning performance for laundry / hard surfaces and an excellent mass efficiency in hard water. The invention includes a process comprising (a) reducing the linearity of an olefin, preferably one having a molecular weight of at least about 126 and not more than about 280. The typical molecular weight range for olefins for a Olefin-based sourcing in the preferred processes can be limited from about 140 to about 196. The linearity reduction or "de-linearization" contradicts the most recent developments in the manufacture of alkylbenzene sulfonate-based detergents, which are aimed at increasing the linearity based on the notion (which the inventors believe is incorrect) that only strict linearity will guarantee environmental compatibility. Essential in the present invention is the notion that procedures for reducing linearity, if combined with a particular type of alkylation later in the process, are not necessarily incompatible to maintain biodegradability and can at the same time lead to important compositional advantages, in terms of yield or final result, of the product based on modified alkylbenzenesulfonate and the products for the consumer that contain them. Technically, it appears that the opportunity to achieve a significant improvement by de-linearization or light branching on alkylbenzenesulfonate based surfactants is very limited. This is explained at least partially by the more than restricted range of total carbon content which is necessary for a good surfactant and good solubility in this particular type of surfactant. Most current LAS, to be useful, they are based on such a narrow range as from about C10 to about C14 for the alkyl portion of the alkylbenzene sulfonate molecule. It is expected that the performance of surfactant will worsen as it de-linearizes the surfactant while remaining in this narrow range of total carbon content even if this improves other physical properties. The reduction in linearity in the present in an important aspect is generally achieved by a step that is selected from: isomerization of the base structure, in the presence of a restricted base structure isomerization catalyst, of a substantially linear olefin preformed to have at least said molecular weight.

Reduction of linearity by isomerization of the base structure of the olefin. Preferred olefins as starting materials for de-linearizing olefins by isomerization of the base structure herein are alpha-olefins having the required molecular weight. The appropriate olefins can be obtained in general from any source. Such olefins include those made by dehydrogenation of a linear paraffin, including especially those made from kerosene processed through the PACOL ™ and OLEX ™ UOP or less preferred by the old Shell (CDC) process; the alpha-olefins generated by polymerization of ethylene, for example by the procedures of Shell, Gulf / Chevron, or Amoco (formerly Ethyl Corp.); the alpha-olefins derived from fractionated wax; the alpha-olefins obtained from the Fischer-Tropsch synthesis, or the internal olefins from the SHOP ™ procedure of Shell. As used, olefins may contain varying amounts of non-monoolefin material, such as paraffins, so long as such materials do not substantially interfere with the isomerization step of the base structure. If the raw materials of the olefin contain unacceptable impurities, such as materials that cause poisoning or other difficulties with the isomerization catalyst of the base structure, the olefin can be purified by known techniques such as distillation. If diene impurities are present in the olefin, these can be removed by the UOP DEFINE ™ process. In general, the isomerization of the olefin base structure herein can be achieved in any manner known in the art. Restricted catalysts for base structure isomerization suitable for various purposes are known and include those selected from the group consisting of zeolites and silicoaluminophosphates (the latter can be simply referred to as "aluminophosphates" elsewhere herein) having one-dimensional pore structures with a size from about 4.2 Angstrom to about 7 Angstrom. Preferred examples of such catalysts include: (i) zeolites having isotypic structure of ferrierite (preferably H-ferrierites); and (ii) non-zeolite types such as silicoaluminophosphates including, but not limited to, ALPO-31, SAPO-11, SAPO-31 and SAPO-41. The ferrierite and SAPO-11 types or any appropriate isotype are especially preferred. The term "isotype" as used herein refers to a catalyst having substantially equivalent structure, particularly with respect to pore dimensions. The inventors have discovered that the catalysts for isomerization of the base structure and the process conditions described in the patent E.U.A. 5,510,306 are especially useful in the present invention. The patent E.U.A. 5,510,306 discloses an active and stable catalyst for isomerizing linear olefins to branched isoolefins with methyl which is provided by (i) mixing (i) a zeolite powder containing at least one zeolite with at least one one-dimensional pore structure having size of pore small enough to retard dimerization of by-products and coal formation and large enough to allow the entry of the linear olefin and allow the formation of the branched isoolefin with methyl; (ii) an alumina-based binder; (iii) water; (iv) at least one acid is selected from monocarboxylic acids and inorganic acids and (v) at least one polycarboxylic acid; (b) forming pellets of the mixture; and (c) calcining the pellet. Preferred catalysts substantially comprise only zeolites with the pore size specified in one dimension. In more detail, the examples of zeolites, aluminophosphates, etc. that can be used to isomerize the base structure of the olefin specified herein are the hydrogenated forms of ferrierite, AIPO-31, SAPO-11, SAPO-31, SAPO-41, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM -50, ZSM-57, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11 , ELAPSO-31, ELAPSO-41, laumontite, cancrinite, ofretite, hydrogenated form of stilbite, and the magnesian or calcia forms of mordenite and partite. Many of the natural zeolites such as ferrierite having an initially reduced pore size can be converted to those forms suitable for isomerizing the olefin base structure in the present invention by removing, for example, the alkali metal or associated alkaline earth metal by ion exchange. ammonium and calcination to produce the substantially hydrogenated form as taught in the US patents 4,795,623 and E.U.A. 4,924,027. Note that the hydrogenated form of the mordenite is not appropriate for this step of the procedure but is useful in the final step of alkylation as will be taught later herein. Particularly useful for the isomerization of the base structure of the olefin in the present is the catalyst prepared in the form of Example 1 of the patent E.U.A. 5,082,953. See also, for example, WO 95/21225 Example 1 and the specification thereof.

Alkylation The invention further includes, after the step of desalination, a monoalkylation step which consists in reacting the de-linearized olefin with an aromatic hydrocarbon which is selected from benzene, toluene and mixtures thereof.

Internal selectivity towards the isomer and selection of an alkylation step The processes of the present require an alkylation step having an internal selectivity towards the isomer in the range from 0 to 40, preferably from 0 to 20, even more preferred from 0 to 10. The internal selectivity towards the isomer or "US" as defined herein is measured for any step of the alkylation process determined by conducting a test of alkylation of benzene by 1-dodecene at a molar ratio of 10: 1. The alkylation is conducted in the presence of an alkylation catalyst up to a conversion of dodecene of at least 90% and formation of monophenyldodecanes of at least 60% Then the internal selectivity towards the isomer determines how: 11 S = 100 * (1-quantity of terminal phenyldodecanes) amount of total phenyldodecanes wherein the quantities are amounts of the products by weight; the amount of terminal phenyldodecanes is the amount of the sum of 2-phenyldodecane and 3-phenyldodecane and the amount of total phenyldodecanes is the amount of the sum of 2-phenyldodecane and 3-, 4-, 5- and 6-phenyldodecane and wherein said Amounts are determined by any known analytical technique for alkylbenzene sulfonates such as gas phase chromatography. See Analytical Chemistry, Nov. 1983, 55 (13), 2120-2126, Eganhouse et al, "Determination of longchain alkylbenzenes in environmental samples by argentation thin-layer chromatography-high resolution gas chromatography and gas chromatography / mass spectrometry. "To calculate the US in accordance with the above formula, the quantities are divided before subtracting the result from one and multiplying by 100. Of course, it should be understood that the specific alkenes used to characterize or prove any step of alkylation in terms of their appropriateness are reference materials which allow a comparison of the alkylation step in the present with known alkylation steps as used in the manufacture of linear alkylbenzene and which enable the practitioner of the invention to decide whether A known alkylation step determined is, or is not, useful in the context of the series of process steps that constitute the present invention In the process of the invention as practiced, the hydrocarbon-based supply material for alkylation normally used is of course that which is specified on the basis of the pas procedural steps. It should also be noted, that all current commercial processes for manufacturing LAS are excluded from the present invention solely on the basis of the US for the alkylation step. For example, the procedures for LAS that are based on aluminum chloride, HF and the like all have a US outside the range specified for the process herein. In contrast, a few alkylation steps described in the literature but not currently applied in the commercial production of alkylbenzene sulfonate have proper US and are useful herein. To better assist the practitioner in determining the US and in deciding whether a particular step of the alkylation process is appropriate for the purposes of the present invention, the following are more particular examples of US determination. As indicated, the benzene alkylation test for 1-dodecene is conducted at a molar ratio of 10: 1 benzene to 1 -dodecene and the alkylation is conducted in the presence of an alkylation catalyst to a dodecene conversion of at least 90% and formation of monofenildodecanos of at least 60%. The alkylation test should generally be conducted in a reaction time of less than 200 hours and at a reaction temperature of about -15 ° C to about 500 ° C., preferably from about 20 ° C to 500 ° C. The pressure and catalyst concentration relative to 1 -dodecene can vary widely. No other solvent is used than benzene in the alkylation test. The process conditions used to determine the US for the catalyst or the alkylation step in question can be based on the literature. The practitioner will generally use appropriate conditions based on a large volume of well-documented alkylation data. For example, the appropriate process conditions for determining whether an alkylation with AICI3 can be used herein are exemplified by a reaction of 5 mol% AICI3 relative to 1 -dodecene at 20-40 ° C for 0.5-1.0 hours in a batch reactor. A test as such demonstrates that an alkylation step with AICI3 is inappropriate for use in the procedure herein. A US of about 48 should be obtained. In another example, an appropriate alkylation test using HF as a catalyst should yield a US of about 60. Thus, neither the alkylation with AICI3 nor the alkylation with HF is within the scope of the invention. this invention. For a medium pore zeolite such as a dealuminized mordenite, the appropriate process conditions for determining the IIS are exemplified by passing 1 -dodecene and benzene at a molar ratio of 10: 1 through a mordenite-based catalyst to a WHSV. of 30 Hr / I at a reaction temperature of about 200 ° C and a pressure of about 14.6 kg / cm2g which should give a US of about 0 for the mordenite-based catalyst. It is expected that the temperatures and pressures for the mordenite alkylation test example (see also detailed examples of the presently present methods hereinafter, are generally more useful for testing zeolites and other form-selective alkylation catalysts. such as H-ZSM-4 a US should be obtained of approximately 18. Clearly both alkylations catalyzed with dealuminated molarite and H-ZSM-4 give US acceptable for the invention, with mordenite being superior.

Alkylation catalyst The attainment of the US required in the step of the alkylation process is made possible by a strictly controlled selection of the alkylation catalysts. Easily several alkylation catalysts are considered as unsuitable. Unsuitable alkylation catalysts include the catalysts of the DETAL® process, aluminum chloride, HF, HF in zeolites, fluorinated zeolite, non-acidic calcium mordenite, and many others. In fact, no alkylation catalyst currently used for alkylation in the commercial production of linear alkylbenzene sulphonates for detergents has yet been found appropriate.

In contrast, the appropriate alkylation catalysts herein are selected from moderately acidic form-selective alkylation catalysts, preferably of the zeolite type. The zeolite in such catalysts for the alkylation step (step (b) is preferably selected from the group consisting of mordenite, ZSM-4, ZSM-12, ZSM-20, offerita, gmelinite and beta zeolite in at least partially form More preferred, the zeolite in step (b) (the alkylation step) is substantially in acid form and is contained in a catalyst pellet containing a conventional binder and wherein said catalyst pellet further contains at least about 1%, preferably at least 5%, more typically from 50% to about 90%, of said zeolite More generally, suitable alkylation catalysts are typically at least partially crystalline, more preferred substantially crystalline not including binders or other materials used to form catalyst pellets, aggregates or mixed materials In addition, the catalyst is typically at least partially acidic. Fully interchanged mordenite alcica, for example, is appropriate where the hydrogenated form of the mordenite is appropriate. This catalyst is useful for the alkylation step identified as step (b) in the claims hereinafter: This corresponds to steps G, H and J in Figures 2-4.

The pores that characterize zeolites useful in the present alkylation process may be substantially circular, such as in cancrinite which has uniform pores of about 6.2 angstroms, or preferably may be somewhat elliptical, such as in mordenite. It should be understood that, in any case, the zeolites used as catalysts in the alkylation step of the present process have a larger pore size intermediate between that of the large pore zeolites, such as the X and Y zeolites and the zeolites of relatively small pore size ZSM-5 and ZSM-11, and preferably between about 6A and about 7A. In effect, zeolite ZSM-5 has been tested and found inoperable in the present invention. The pore size and crystal structure dimensions of certain zeolites are specified in ATLAS OF ZEOLITE STRUCTURE TYPES by WM Meier and DH Olson, published by the Structure Commission of the International Zeolite Association (1978 and later editions) and distributed by Polycrystal Book Service , Pittsburgh, Pa. The zeolites useful in the alkylation step of the present processes generally have at least 10% of the cationic sites thereof occupied by anions other than the alkali or alkaline earth metals. Typically, but not limited to, the replacement ions include ammonium, hydrogen, rare earth, zinc, copper and aluminum. Of this group, particular preference is given to ammonium, hydrogen, rare earths or combinations thereof. In a preferred embodiment, the zeolites are converted to the predominantly hydrogenated form, generally by replacing the alkali metal ion or other ion originally present with hydrogen ion precursors., for example ammonium ions, which after calcining give the hydrogenated form. This exchange is conveniently carried out by contacting the zeolite with an ammonium salt solution, for example, ammonium chloride, using well-known ion exchange techniques. In certain preferred embodiments, the degree of replacement is such that a zeolite material is produced in which at least 50% of the cationic sites are occupied by hydrogen ions. The zeolites can be subjected to various chemical treatments, including alumina extraction (dealuminization) and combination with one or more metal components, particularly the metals of groups IIB, III, IV, VI, VII and VIII. It is also contemplated that the zeolites may, in some cases, be desirably subjected to thermal treatment, including vaporization or calcination in air, hydrogen or an inert gas, for example nitrogen or helium. A suitable modifying treatment imposes the vaporization of the zeolite by contact with an atmosphere containing from about 5 to about 100% steam at a temperature of about 250 ° C to 1000 ° C. The vaporization can last for a period of between about 0.25 and about 100 hours and can be carried out at pressures ranging from subatmospheric pressures to several hundred atmospheres.

In practicing the desired alkylation step of the present process, it may be useful to incorporate the intermediate pore size crystalline zeolites described above into another material, for example a binder or a temperature resistant matrix and other conditions used in the process. Such matrix materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica and / or metal oxides. The matrix materials may be in the form of gels including mixtures of silica and metal oxides. The latter can be either naturally or in the form of gels or gelatinous precipitates. Clays present in nature that can be mixed with zeolites include those from the families of montmorillonite and kaolin, whose families include sub-bentonites and kaolins commonly known as clays Dixie, McNamee-Georgia and Florida or others in the which the main constituent mineral is haloisite, kaolinite, diquita, nacrite or anaoxite. Such clays can be used in the raw state as originally extracted from the mine or initially subjected to calcination, acid treatment or chemical modification. In addition to the above materials, the intermediate pore size zeolites used herein may be combined with a porous matrix material, such as alumina, silica-alumina, silica-magnesium dioxide, silica-zirconium dioxide, silica-dioxide thorium, silica-beryllium dioxide and silica-titanium dioxide, as well as ternary combinations, such as silica-aluminum dioxide-thorium dioxide, silica-aluminum dioxide-zirconium dioxide, silica-aluminum dioxide-magnesium dioxide , and silica-magnesium dioxide-zirconium dioxide. The matrix can be in the form of co-gel. The relative proportions of the finely divided zeolite and the inorganic oxide gel matrix can vary widely, the zeolite content being between about 1 to about 99% by weight and more generally in the range of about 5 to about 80% by weight of the mixed material. A group of zeolites that includes some useful for the alkylation step herein have a silica: alumina ratio of at least 10: 1, preferably at least 20: 1. The silica: alumina ratios referred to in this specification are structural or framework relationships, that is, the ratio for the tetrahedron SiO4 to the AIO. This relationship can vary from the silica: alumina ratio determined by various physical and chemical methods. For example, a non-detailed chemical analysis may include the determination of aluminum, which is present in the form of cations associated with the acid sites in the zeolite, thus giving a low silica: alumina ratio. Similarly, if the ratio is determined by thermogravimetric analysis of ammonia desorption, a low ammonia titre can be obtained if the cationic aluminum prevents the exchange of the ammonium ions on the acid sites. These disparities are particularly problematic when certain treatments such as the desaluminization methods described below are employed which results in the presence of free ionic aluminum of the zeolite structure. Therefore, care must be taken to ensure that the ratio of the silica: alumina structure is determined correctly. The beta zeolite suitable for use in the present (but less preferred than H-mordenite) is described in the patent E.U.A. Do not. 3,308,069 to which reference is made for details of this zeolite and its preparation. Such zeolite in acid form can also be commercially available as Zeocat PB / H from Zeochem. When the zeolites have been prepared in the presence of organic cations they are catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations originating from the formation solution. These can be activated by heating them in an inert atmosphere at 540 ° C for 1 hour, for example, followed by exchange in basic medium with ammonium salts and then calcination at 540 ° C in air. The presence of organic cations in the formation solution may not be absolutely essential for the formation of the zeolite; but it seems to be that it favors the formation of this special type of zeolite. Some natural zeolites can sometimes be converted to zeolites of the desired type by various activation methods and other treatments such as exchange in basic medium, vaporization, alumina extraction and calcination. The zeolites preferably have a density of crystalline structure, in the dry hydrogenated form, not substantially below about 1.6 g. cm-3 The dry density for known structures can be calculated from the number of silicon atoms plus the aluminum atoms per 1000 Angstroms, cubic, as given, for example on page 19 of the article on structure of zeolite by W.M. Meier included in "Proceedings of the Conference on Molecular Sieves, London, April 1967", published by the Society of Chemical Industry, London 1968. Reference is made to this document for a discussion of crystal structure density. An additional discussion of the crystal structure density, together with values for some typical zeolites, is given in the patent E.U.A. No. 4,016,218, to which reference is made. When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogenated form, generally by intermediate formation of the ammonium form as a result of ammonium ion exchange and calcination of the ammonium form to give the hydrogenated form. It has been found that although the hydrogenated form of the zeolite catalyzes the reaction successfully, the zeolite may also be partially in the alkali metal form. EP 466,558 discloses an alkylation catalyst of the mordenite acid type which can also be used herein which has a total atomic ratio of Si / Al of 15-85 (15-60), Na content in weight less than 1000 ppm (preferably less than 250 ppm), having a minimum or no content of extra Al species, and an elementary mesh volume below 2.760 nm3. The patent E.U.A. do not. No. 5,057,472 useful for preparing alkylation catalysts herein refers to the concurrent dealumination and ion exchange of a zeolite containing acid-stable Na ion, preferably mordenite affected by contact with a 0.5-3 HNO3 solution (preferably 1 -2.5) M containing enough NH4NO3 to completely exchange the Na ions for NH4 ions and H ions. The resulting zeolites can have a SiO2: AI2O3 ratio of 15-26 (preferably 17-23): 1 and preferably calcined to at least partially convert the NH-j / H form to an H form. Optionally, although not necessarily particularly desired in the present invention, the catalyst may contain a Group VIII metal (and optionally also an inorganic oxide) together with the calcined zeolite of the '472 patent. Another catalyst based on acidic mordenite useful for the alkylation step herein is described in the patent E.U.A. 4,861, 935 which refers to a hydrogenated mordenite incorporated with alumina, the composition having a surface area of at least 580 m2 / g. Other acid mordenite-based catalysts useful for the alkylation step herein include those described in US Pat. 5,243,116 and E.U.A. 5,198,595. Even another alkylation catalyst useful herein is described in the patent E.U.A. 5,175,135 which is a zeolite based on acid mordenite having a silica / alumina molar ratio of at least 50: 1, a symmetry index of at least 1.0 as determined by X-ray diffraction analysis, and a porosity such that the total pore volume is in the range of about 0.18 cc / g to about 0.45 cc / g and the ratio of the combined meso- and macropore volume to the total pore volume is from about 0.25 to about 0.75. Particularly preferred alkylation catalysts herein include the Zeocat ™ FM-8 / 25H acid mordenite based catalysts available from Zeochem; CBV 90 A available from Zeolyst International, and LZM-8 available from UOP Chemical Catalysts. More generally, any alkylation catalyst can be used herein with the proviso that the alkylation step meets the requirements of internal selectivity towards the isomer identified above.

PROCESSES BASED ON PARFFINIC SUPPLY MATERIALS In another aspect, the present invention relates to a process for preparing modified surfactant-based surfactant suitable for use in cleaning products, said process (a) comprising a step of or provide) a reduced linearity alkylating agent selected from an olefin having a molecular weight of at least about 126 and not more than about 280 and produced by a sequence of steps comprising: (i) isomerizing the base structure of a paraffin linear having molecular weight of n + 2 in which n is said molecular weight of said olefin; (ii) dehydrogenated paraffin; and (b) a monoalkylation step having an internal selectivity to the isomer of about 0 to 40 which comprises reacting the product of step (a) with an aromatic hydrocarbon which is selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst. The alkylation catalyst is identical to the alkylation catalyst of step (b) in the process defined above starting from olefinic supply materials. The product of this process can be sulfonated, neutralized and combined or mixed with ingredients for cleaning products as defined by the process of the invention on the basis of olefinic supply materials described herein.

Isomerization of the base structure of the linear paraffin The preferred starting paraffinic materials to de-linearize paraffins by isomerization of the base structure herein are linear paraffins having the required molecular weight. Suitable paraffins can be obtained more generally from any source. As used, the paraffins may contain, in addition to the linear paraffin, varying amounts of other materials, such as isoparaffins or olefins, as long as such materials do not interfere materially with the isomerization step of the base structure. If the paraffinic raw materials contain unacceptable impurities, such as materials that cause poisoning or other difficulties with the base structure isomerization catalyst, the linear paraffin can be purified by standard techniques. known as distillation or catalytic hydrogenolysis to remove impurities containing sulfur. Suitable paraffinic sourcing materials should contain linear paraffins and such sourcing materials are commonly based on kerosene treated by the UOP MOLEX ™ process. In general, any catalyst suitable for branching with alkyl, preferably for branching with methyl, a linear paraffin is useful in the process herein. Catalysts for isomerizing the preferred base structure for this step include (i) zeolites having isotypic structure of ferrierite (preferably H-ferrierites); (see for example U.S. Patent 5,510,306) and (ii) ALPO-31, SAPO-11, SAPO-31 and SAPO-41. Catalyst systems containing SAPO-11 are preferred and can include both Pt-SAPO-11 and Pd-SAPO-11 although the platinum form is preferred. See patent E.U.A. 5,246,566 and S.J. Miller, Microporous Materials, Vol.2 (1994) 439-449; the latter reference also provides a comparison with some other catalysts to isomerize useful linear paraffin which are listed in detail but none of such catalysts is as effective as systems containing SAPO-11. Despite the apparent inapplicability of a document on the dewaxing of lubricating oil, Miller is insightful in teachings that have been found applicable to the manufacture of alkylbenzene sulfonate. For example, on page 440 of the aforementioned Microporous Materials article, Miller teaches a low selectivity of SAPO-11 for gem-dimemethyl species with preference toward branching with methyl separated by more than one carbon atom. It is expected that the use of SAPO-11 in the isomerization step of the paraffin base structure of the present process will confer exactly such properties to the branched hydrocarbon used to make modified alkyl benzene-based surfactants, and alkylbenzene sulphonates and cleaning compositions for the consumer in the present.

Dehydration of isomerized paraffin in the base structure In general, the dehydrogenation step of the isomerized paraffin in the base structure in the process herein can be achieved using any of the known dehydrogenation catalyst systems or "conventional dehydrogenation catalysts" including the described in the Surfactant Science Series references cited in the prior art as well as in "Detergent Manufacture Including Zeolite Builders and Other New Materials", Ed. Stting, Noyes Data Corp., New Jersey, 1979 and other dehydrogenation catalyst systems, for example those commercially available through UOP Corp. Dehydrogenation can be performed in the presence of hydrogen and a precious metal-based catalyst is commonly present although dehydrogenation systems free of precious metal and without hydrogen such as a zeolite system can alternatively be used. / air s in which precious metals are present.

As is well known, the dehydrogenation can be complete or partial, more typically partial. When it is partial, this step forms a mixture of unreacted olefin and paraffin. Such a mixture is a suitable supply material for the alkylation step of the present process.

Alkylation in Paraffin-Based Processes The alkylation step and the alkylation catalysts in paraffin-based process herein are identical to the alkylation step and the alkylation catalysts described in conjunction with the olefin-based process described in detail hereinbefore.

Post Alkylation Steps The present invention also encompasses a process in accordance with any of the above aspects or embodiments (whether they are based on paraffin or olefin) having the additional steps of (c) sulfonating the product of step (b); and one or more steps that are selected from (d) neutralizing the product of step (c); and (e) mixing the product of step (c) or (d) with one or more adjunct materials for cleaning products, whereby a cleaning product is formed.

Distillation of modified alkylbenzenes Optionally, depending on the supply solution and the precise sequence of steps used, the present process may include the distillation of modified alkylbenzenes, for example to remove unreacted starting materials, paraffins, excesses of benzene and the like. Any conventional distillation apparatus can be used. The general practice is similar to that used for the distillation of commercial linear alkylbenzenes (LAB). Suitable distillation steps are described in the Surfactant Science Series review of alkylbenzene sulfonate manufacture mentioned above.

Sulfonation and treatment In general, the sulfonation of alkylbenzenes modified in the present process can be achieved using any of the well-known sulphonation systems, including those described in the volume "Detergent Manufacture Including Zeolite Builders and Other New Materials" as well as in the review Surfactant Science Series of alkylbenzene sulfonate manufacture mentioned hereinabove. Common sulfonation systems include sulfuric acid, chlorosulfonic acid, oil, sulfur trioxide and the like. Sulfur trioxide / air is especially preferred. Details of sulfonation using a suitable air / sulfur trioxide mixture are provided in US 3,427,342, Chemithon.

Any convenient treatment step can be used in the present process. The common practice is to neutralize after sulfonation with any suitable alkali. In this way, the neutralization step can be carried out using an alkali selected from sodium, potassium, ammonium, magnesium and substituted ammonium and mixtures thereof. Potassium can aid solubility, magnesium can promote performance in soft water, and substituted ammonium can be useful for formulating specialty variations of the present surfactants. Alkali in the form of sodium such as sodium hydroxide is the most commonly used. The most preferred alkali is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate and mixtures thereof. The invention encompasses any of the forms derived from the modified alkylbenzenesulfonate surfactants as produced by the present process, and their use in consumer product compositions. Alternatively, the acid form of the present surfactants can be added directly from the acidic cleaning products, or can be mixed with cleaning ingredients and then neutralized.

Mixed Modes In a preferred embodiment, prior to the sulfonation step in the present process, the modified alkylbenzene which is the product of said step (c) is mixed with a linear alkylbenzene, such as linear C 10 -C 14 alkylbenzene, produced by a process conventional. In another embodiment, at any step subsequent to said sulfonation step, modified alkylbenzenesulfonate (acid form or neutralized form) produced according to the present process is mixed with a linear alkylbenzenesulfonate, such as linear C 10 -C 14 alkylbenzenesulfonate (acid form or neutralized) produced by a conventional procedure. In these mixed modalities, the mixtures can be made at a weight ratio of linear and modified alkylbenzenes or their derivatives of 100: 1 to 1: 100. A preferred process has a ratio of modified alkylbenzene compounds to linear alkylbenzene from about 10:90 to about 50:50. Another preferred process has a ratio of modified alkylbenzene compounds to linear alkylbenzene from about 51:49 to about 92: 8.

Formulation in cleaning products The present invention also encompasses a cleaning product formed by the present process, comprising: a) from about 0.1% to about 99.8%, most typically up to about 50%, of a modified alkylbenzene sulfonate surfactant as the preparation in the present and b) of about 0.00001%, very typically at least about 1% to about 99.9%, of one or more of said adjunct materials for cleaning product. The attached materials can vary widely and can therefore be used at widely varying levels. For example, detersive enzymes such as proteases, amylases, cellulases, lipases and the like, as well as bleach catalysts including macrocyclic types having manganese or similar transition metals, all useful in laundry and cleaning products can be used herein. very low or, less commonly, higher levels. Other adjunct materials for cleaning products suitable herein include bleaches, especially oxygenated bleaches including activated forms and catalyzed with bleach activators such as nonanoyloxybenzenesulfonate and / or tetracetylethylenediamine and / or any of their derivatives or derivatives of phthaloylimidoperoxycaproic acid or others. mido- or amido-substituted bleach activators including the lactam types, or very generally any mixture of hydrophilic and / or hydrophobic bleach activators (especially acyl derivatives including those of the substituted Cβ-C-iβ-oxybenzenesulfonates); preformed perishes related to, or based on any of the aforementioned bleach activators, builders including insoluble types such as zeolites, including zeolites A, P and so-called maximum aluminum P, as well as soluble types such as phosphates and polyphosphates, any of the hydrated silicates, water-soluble or insoluble in water, 2,2'-oxydisuccinates, tartratesuccinates, glycolates, NTA and many other ethercarboxylates or citrates, chelating agents including EDTA, S, S'-EDDS, DTPA and phosphonates, polymers, copolymers and water-soluble terpolymers, dirt release polymers, surfactant coagents including any of the known anionic, cationic, non-ionic or zwitterionic types, optical brighteners, processing aids such as crispers and / or fillers, solvents, antiredeposition agents, silicone / silica and other foam suppressors, hydrotrope s, perfumes or pro-perfumes, dyes, photobleaches, thickeners, simple salts and alkalis such as those based on sodium or potassium that include hydroxides, carbonates, bicarbonates and sulphates, and the like. When combined with the modified alkylbenzenesulfate surfactants of the present process, any of the anhydrous, hydrated, water-based or solvent-based cleaning products are readily available as granules, liquids, tablets, powders, flakes, gels, extrudates, encapsulated or bagged or similar forms. Accordingly, the present invention also includes the different cleaning products made possible or formed by any of the methods described. These can be used in individual dosage forms, used by hand or machine, or can be dosed continuously in any suitable cleaning device or delivery device.

Cleaning products in detail The references cited herein are incorporated by reference. The surfactant compositions prepared by the methods of the present invention can be used in a wide range of consumer cleaning product compositions including powders, granules, gels, pastes, tablets, bags, bars, types provided in double compartment containers, spray or foam detergents and other homogeneous or multiphasic forms of cleaning product for the consumer. They can be used or applied by hand and / or can be applied in unitary or freely alterable dosing, or by automatic means of supply, or are useful in apparatuses such as washing machines or dishwashers, or can be used in institutional cleaning contexts, including, for example , for personal cleaning in public facilities, for washing bottles, for cleaning surgical instruments or for cleaning electronic components. They may have a wide pH range, for example from about 2 to about 12 or more, and may have a broad scale of alkalinity reserve which may include very high alkalinity reserves such as in drainage uncovering uses in which they may several grams of NaOH equivalent per 100 grams of formulation are present, varying through the 1-10 grams of NaOH equivalent and the mild or low alkalinity scales of liquid hand cleaners, to the acidic side such as in the cleaners hard surface acids. The types of detergents of both high and low foaming are covered. Cleaning compositions for consumer products are described in: "Surfactant Science Series", Marcel Dekker, New York, volumes 1-67 and later. Particular liquid compositions are described in detail in volume 67, "Liquid Detergents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9 incorporated herein by reference. The most classic formulations, especially granular types, are described in "Detergent Manufacture ncluding Zeolite Builders and Other New Materials", Ed. M. Sitting, Noyes Data Corporation, 1979 incorporated herein by reference. See also Kirk Othmer's Encyclopedia of Chemical Technology. The consumer product cleaning compositions herein include, but are not limited to: Light duty liquid detergents (LDL) These compositions include compositions for LDL having magnesium ions the best surfactant (see, for example, WO 97/00930 A, GB 2,292,562 A, US 5,376,310, US 5,269,974, US 5,230,823, US 4,923,635, US. 4,681, 704; US 4,316,824; US 4,133,779) and / or organic diamines and / or various foam stabilizers and / or foam boosters such as amine oxides (see, for example, US 4,133,779) and / or sensation modifiers of the skin surfactant, emollient and / or enzymatic type, including proteases; and / or antimicrobial agents; the most comprehensive patent listings are given in Surfactant Science Series, vol. 67, pages 240-248. Heavy Duty Liquid Detergents (HDL) These compositions include both so-called "structured" or multi-phase (see, for example, US 4,452,717, US 4,526,709, US 4,530,780, US 4,618,446, US 4,793,943, US 4,659,497, US 4,871, 467; 4,891, 147; US 5,006,273; US 5,021, 195; US 5,147,576; US 5,160,655) as "unstructured" or isotropic liquid types, and can generally be aqueous or non-aqueous (see, for example, EP 738,778 A; WO 97 00937 A, WO 97/00936 A, EP 752,466 A, DE 19623623 A, WO 96/10073 A, WO 96/10072 A, US 4,647,393, US 4,648,983, US 4,655,954, US 4,661, 280, EP 225,654, US 4,690,771; US 4,744,916, US 4,753,750, US 4,950,424, US 5,004,556, US 5,102,574, WO 94/23009, and can be with bleach (see, for example, US 4,470,919, US5,250,212, EP 564,250, US 5,264,143, US 5,275,753.; US 5,288,746; WO 94/11483; EP 598,170; EP 598,973; EP 619,368; US 5,431,848; US 5445,756) and / or enzymes (see, for example, US 3,944,470, US 4,111,855, US 4,261,868, US 4,287,082, US 4,305,837, US 4,404,115, US 4,462,922, US 4,529,5225, US 4,537,706, US 4,537,707, US 4,670,179, US 4,842,758, US 4,900,475, US 4,908,150, US 5,082,585, US 5,156,773, WO 92/19709, EP 583,534, EP 583,535, EP 583,536, WO 94/04542, US 5,269,960, EP 633,311, US 5,422,030, US 5,431, 842.; US 5,442,100) or without bleach and / or enzymes. Other patents that refer to liquid heavy duty detergents are tabulated or listed in Surfactant Science Series, vol. 67, pages 309-324.

Heavy Duty Granular Detergents (HFG) These compositions include both so-called "compact" or agglomerated or otherwise non-spray dried, as well as so-called "spongy" or spray-dried. Both the fofated and non-phosphate types are included. Such detergents may include the most common anionic surfactant-based types or may be so-called "nonionic surfactant" types in which commonly the nonionic surfactant is held in, or on an absorbent material such as zeolites or other porous inorganic salts. The manufacture of HDG's is described, for example, in EP 753,571 A; WO 96/38531 A; US 5,576,285; US ,573,697; WO 96/34082 A; US 5,596,645; EP 739,977 A; US 5,565,422; EP 737,739 A; WO 96/27655 A; US 5,554,587; WO 96/25482 A; WO 96/23048 A; WO 96/22352 A; EP 709,449 A; WO 96/09370 A; US 5,496,487; US 5,489,392 and EP 394,608A.

"Deterswetting" (STW) These compositions include the different types of softening product during washing granulates or liquids (see, for example, EP 753,596 A; US 4,140,641; US 4,639,321, US 4,751, 008; EP 315,126; US 4,844,821; US 4,844,824; US 4,873,001; US 4,911,852; US 5,017,296; EP 422,787) and in general may have organic (for example, quaternary) or inorganic (for example, clay) softeners.

Hard Surface Cleaners (HSC) These compositions include all-purpose cleaners such as cream cleaners and all-purpose liquid cleaners; all-purpose spray cleaners including glass and tile cleaners, and bleach spray cleaners; bath cleaners including mold removal, those containing bleach, antimicrobials, acids, neutrals and basics. See, for example, EP 743,280 A; EPT43.279 A. Acid cleaners include those of WO 96/34938 A.

Soap bars and / or laundry bars (BS &HW) These compositions include bars for personal cleaning as well as so-called laundry bars (see, for example, WO 96/35772 A); including both synthetic and soap-based types and softener types (see, US 5,500,137 or WO 96/01889 A); said compositions may include those made by common soapmaking techniques such as extrusion and / or less conventional techniques such as casting, absorbing surfactant on a porous support or the like. Other soap bars are also included (see, for example, BR 95/2668, WO 96/04361 A, WO 96/04360 A, US 5,540,852). Other detergents for hand washing include those as described in GB 2,292,155 A and WO 96/01306 A.

Shampoos and conditioners (S &C) See, for example, WO 96/37594 A; WO 96/17917 A; WO 96/17590 A; WO 96/17591 A. Said compositions generally include both simple shampoos and so-called "two-in-one" and "with-conditioner" types.

Liquid Soaps (LS) These compositions include both so-called "antibacterial" and conventional types, as well as those with or without skin conditioners, and include types suitable for use in pumping dispensers and by other means such as devices embedded in the wall used institutionally.

Special Purpose Cleaners (SPC) These include home dry cleaning systems (see, for example, WO 96/30583 A, WO 96/30472 A, WO 96/30471 A, US 5,547,476, WO 96/37652 A); products for pretreatment with laundry bleach (see EP 751, 210 A); products for pretreatment of fabrics (see, for example, EP 752,496 A); types of liquid detergent for fine fabrics, especially the variety of high foaming; rinse aid for dishwashing; liquid whiteners including both chlorine and oxygenated bleach, and disinfectants, mouthwashes, denture cleansers (see, for example, WO 96/19563 A; WO 96/19562 A); cleaning agents or shampoos for cars or carpets (see, for example EP 751, 213 A; WO 96/15308 A), hair rinses, bath gels, foam baths and personal care cleaners (see, for example, WO) / 37595 A, WO 96/37592 A, WO 96/37591 A, WO 96/37589 A, WO 96/37588 A, GB 2,297,975 A, BG 2,297,762 A, GB 2,297,761 A, WO 96/17916 A, WO 96/12468 A) and metal cleaners; as well as cleaning aids such as bleach additives and "stain sticks" or other types of pretreatment including special foam cleaners (see, for example, EP 753,560 A; EP 753,559 A; EP 753,558 A; EP 753,557 A; 753,556 A) and anti-fogging treatments by sol (see WO 96/03486 A, WO 96/03481 A, WO 96/03369 A). Detergents with durable perfume (see, for example, US 5,500,154; WO 96/02490) are becoming increasingly popular.

Process integration The present procedure can be integrated with current LAB manufacturing processes in any convenient manner. For example, a conventional plant can be changed to produce the modified alkylbenzenes in their entirety. Alternatively, depending on the desired volumes or available supply solutions, for example as effluents from the LAB process or based on the proximity of sources of supply material of the petrochemical industry, a plant for the manufacture of the present modified alkylbenzenes can be constructed as a complement or addition to an existing LAB installation, or as an individual plant. Both intermittent and continuous operation of the present procedure are glimpsed. The present invention should not be considered limited by the specific details of its illustration in the description, including the examples given for illustration below. More generally, the present invention should be taken as encompassing any consumer cleaning composition comprising any surfactant product of any type in which the hydrophobe of the surfactant has been modified by an approach using the essential teachings of the present process. The present teachings, especially with respect to the de-linearization approach, are believed to be reapplicable, for example, to the manufacture of modified alkyl sulfates and other surfactants.

Other embodiments The present invention is not limited to the specific embodiments described so far. Thus, a method for improving the cleaning performance of a consumer cleaning product containing alkylarylsulfonate surfactant is comprised in, this method comprises a) at least one step (one step being one or more steps) ) of deslinealization of a C-C16 alkylarene (the arene being benzene or less preferably toluene, xylene, naphthalene, or mixtures thereof) to at least a minimum degree of about 0.1 methyl portions per molecule of said alkylarene and a maximum degree of about 1 to about 2.5 methyl portions per molecule of said alkylarene, said step comprises at least one linearization reduction step carried out before, in parallel with, or subsequent to a coupling step of the precursor portions of alkyl and the aryl precursor portions of said alkylarene (these precursors being illustrated by the olefins and / or paraffins described as materials starting for the process described hereinabove); b) at least one step of sulfonating the highly branched alkylarene product of step a); and c) at least one step of formulating the slightly branched alkylarylsulfonate surfactant product of step b) in the form of acid or salt in a cleaning composition. Said method includes very particularly the method in which step a) forms 1-phenyl isomers of said alkylarene; the method in which step a) forms 2-phenyl isomers of said alkylarene to an advantageous degree, for example of at least about 60%; the method in which step a) forms at least two homologs of said alkylarenes wherein said alkyl portions attached to said aryl portions contain from 10 to 16 carbon atoms, most preferably from 11 to 14 carbon atoms in total and in where each of said homologs (any two "homologs" having the same structure excluding isomers but different by having a different number of carbons in the indicated scale of total carbon atoms) comprises at least two positional isomers with respect to the bond of said methyl portions to the rest of the alkyl portions in said alkylarenes. Also included is the method in which step a) is carried out without being based on aluminum chlorine catalysts or containing iron; the method wherein step a) is carried out without relying on the polymerization of propylene strongly catalyzed with conventional acid, such as polymerization catalyzed with HF or aluminum chloride; the method wherein more than 20% of the alkylarene molecules produced in step a) have a methyl moiety; the method wherein not more than about 20% of the alkylarene product of step a) has two or more methyl portions; the method in which step a) includes a skeletal rearrangement step conducted after the formation of said alkylarene; the method in which step a) includes an isomerization step carried out in parallel with the formation of said alkylarene; the method in which step a) comprises Fischer-Tropsch chemistry and / or uses Synthol olefins; the method in which step a) is independent of FischerTropsch chemistry and / or is not based on Synthol olefins; the method in which step a) includes the use of a fluoride-free dealuminized mordenite catalyst; the method in which step a) includes the use of a ferrierite catalyst and the method in which step a) produces a molecular weight distribution that is consistent with the presence in said alkylarylene of alkylarylene molecules having a Total carbon atoms that include both the pairs and non-carbon totals. Most preferably, any of the methods mentioned are based on an alkylation step having an internal isomer selectivity on the scale of 0 to 40, most preferably 0 to 20 or less. In addition, any cleaning composition comprising an improved surfactant composition produced by any of said methods is included herein.

EXAMPLE 1 Modified alkyl benzene sulfonate surfactant prepared by linear skeletally isomerized olefin Step a): At least partial reduction of the linearization of an olefin (by skeletal olefin isomerization carried out at chain lengths suitable for the detergency of the cleaning product A mixture of 1 -decene, 1-undecene, 1 -dodecene and 1-tridecene (for example available from Chevron) at a weight ratio of 1: 2: 2: 1 is passed over a Pt-SAPO catalyst at 220 ° C and any suitable LHSV, for example 1.0 The catalyst is prepared from Example 1 of US Pat. No. 5,082,956, see WO 95/21225, for example, Example 1 and the description thereof The product is a slightly branched, skeletally isomerized olefin having a scale of suitable chain lengths to make a surfactant of alkylbenzenesulfonate to be incorporated into a consumer cleaning composition, very generally the temperature in this step can be from about 200 ° C to about 400 ° C, preferably around 230 ° C to approximately 320 ° C. The pressure is typically from about 1.05 kg / cm 2 nanometer to about 140.6 kg / cm 2 nanometer, preferably about 1.05 kg / cm 2 nanometer to about 70.3 kg / cm 2 nanometer, most preferably about 1.05 psig kg / cm 2 nanometer to about 42.2 kg / nanometric cm2. Hydrogen is a suitable pressurizing gas. The space velocity (LHSV or WHSV) is suitably from about 0.05 to about 20. Low pressure and low space velocity between hours provide improved selectivity, more isomerization and less cracking. It is distilled to remove any volatile material that boils at up to approximately 40 ° C / 10mmHg.

Step b): Alkylation of the product from step (a) using an aromatic hydrocarbon To a glass autoclave liner is added one molar equivalent of the slightly branched olefin mixture produced in step a), molar equivalents of benzene and 20% by weight, based on the olefin mixture, of a shape selective zeolite catalyst (acid mordenite catalyst Zeocat ™ FM-8 / 25H). The glass liner is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with 17.58 kg / cm2 nanometer N2) and then loaded at 70.3 kg / cm2 nanometer N2. With mixing, the mixture is heated at 170-190 ° C for 14-15 hours, after which time it is cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst and concentrated by distillation of the unreacted starting materials and / or impurities (eg, benzene, olefin, paraffin, trace materials, the useful materials being recirculated if desired) to obtain a liquid product almost colorless and transparent. The product formed is a desirable modified alkylbenzene mixture which can, as an option, be sent to a far manufacturing facility where additional steps of sulfonation and incorporation in consumer cleaning compositions can be achieved.

Step c): Sulfonation of the product from step b) The modified alkylbenzene mixture from step b) is sulfone with one equivalent of chlorosulfonic acid using methylene chloride as the solvent. The methylene chloride is distilled.

Step d): Neutralization of the product from step c) The product of step c) is neutralized with sodium methoxide in methanol and the methanol is evaporated to give modified alkylbenzene sulfonate, sodium salt mixture.

EXAMPLE 2 Modified alkylbenzene sulfonate surfactant prepared by linear skeletally isomerized olefin The procedure of Example 1 is repeated, except that the sulphonation step c), uses sulfur trioxide (without methylene chloride solvent) as the sulfonation agent. Details of the sulfonation using a suitable mixture of air / sulfur trioxide are provided in US 3,427,342, Chemithon. In addition, step d) uses sodium hydroxide instead of sodium methoxide for neutralization.

EXAMPLE 3 Modified alkylbenzene sulfonate surfactant prepared by linear isolized isoguenetically olefin Step a): At least partial reduction of the linearization of an olefin A slightly branched olefin mixture is prepared by passing a mixture of C11-C12 and C13 mono-olefins in the weight ratio of 1: 3: 1 over H-catalyst ferrierite at 430 ° C. The method and catalyst of US 5,510,306 can be used for this step. It is distilled to remove any volatile material that boils up to approximately 40 ° C / 10 mmHg.

Step (b): Alkylation of the product of step a) using an aromatic hydrocarbon To a glass autoclave liner is added one molar equivalent of the slightly branched olefin mixture of step a), 20 molar equivalents of benzene and 20% of weight, based on the olefin mixture, of a shape selective zeolite catalyst (acid mordenite catalyst Zeocat ™ FM-8 / 25H). The glass lining is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with 17.58 kg / cm2 nanometer N2, and then loaded at 70.3 kg / cm2 nanometer N2. With mixing, the mixture is heated at 170-190 ° C overnight for 14-15 hours, after which time it is cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. Benzene is distilled and recirculated, the volatile impurities also being removed. A nearly colorless or colorless transparent liquid product is obtained.

Step c) Sulfonation of the product of step b) The modified alkylbenzene mixture of step b) is sulfone with one equivalent of chlorosulfonic acid using methylene chloride as the solvent. The methylene chloride is distilled.

Step d): Neutralization of the product from step c) The product from step c) is neutralized with sodium methoxide in methanol and the methanol is evaporated to give the modified alkylbenzenesulfonate, sodium salt mixture.

EXAMPLE 4 Modified alkylbenzene sulfonate surfactant prepared by linear isoglyethically isomerized olefin The procedure of Example 3 is repeated except that the sulfonation step c) uses sulfur trioxide (without methylene chloride solvent) as the sulfonation agent. Details of the sulfonation using a suitable mixture of air / sulfur trioxide are provided in US 3,427,342, Chemithon.

EXAMPLE 5 Cleaning composition The procedure of step 1 is repeated except that the product of step d) is further treated by the following additional step e).

Step e): Incorporation of the product from step d) into a 10% cleaning composition. By weight of the product of step d) it is combined with 90% by weight of a compact and agglomerated laundry detergent granule.

EXAMPLE 6 Modified alkylbenzene sulfonate surfactant prepared by linear skeletally isomerized olefin In example 1, step b) is replaced with the following: Step b): Aligilation of the product from step a) using an aromatic hydrocarbon To a glass autoclave liner is added one molar equivalent of the slightly branched olefin mixture from step a), 20 molar equivalents of benzene and 20%, in based on the weight of the olefin mixture, of a shape selective zeolite catalyst (zeolite beta acid ZEOCAT ™ PB / H). The glass lining is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with 17.58 kg / cm2 nanometer N2, and then loaded at 70.3 kg / cm2 nanometer N2. With mixing, the mixture is heated at 145-150 ° C overnight for 14-15 hours, after which time it is then cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. Benzene is distilled and recirculated, removing also the volatile impurities. A transparent colorless or colorless liquid product is obtained.

EXAMPLE 7 Modified alkoxybenzene sulfonate surfactant prepared by linear isoglyethically isomerized olefin The procedure of Example 6 is repeated except that the selective zeolite catalyst of step b) is replaced with HZSM-12 as described in US 3,832,449 and the reaction temperature for step b) is about 200-220 ° C. .

EXAMPLE 8 Modified alkylbenzene sulfonate surfactant prepared by linear isoglyethically isomerized olefin The procedure of Example 1 is followed except that in step b) the molar ratio of benzene to olefin mixture is 5: 1.

EXAMPLE 9 Modified alkyl benzene sulfonate surfactant prepared by linear skeletally isomerized olefin The procedure of Example 1 is repeated, except that the neutralizing agent of step d) is sodium hydroxide instead of sodium methoxide.

EXAMPLE 10 Modified alkyl benzene sulphonate surfactant prepared by linear olefin, isolistically isomerized The procedure of Example 1 is repeated, except that the sulfonation agent of step c) is oil, and the neutralizing agent of step d) is potassium hydroxide instead of sodium methoxide.

EXAMPLE 11 Modified alkylbenzene sulfonate surfactant prepared by paraffin skeletal isomerization Step (ai) A mixture of n-undecane, n-dodecane, n-tridecane, 1: 3: 1 by weight, is isomerized on Pt-SAPO-11 for a better conversion at 90% at a temperature of 300-340 ° C, at 70.3 kg / cm2 nanometer under hydrogen gas, with a space velocity per hour of weight in the range of 2-3 and 30 moles of H2 / mole of hydrocarbon. More details of said isomerization are given by S.J. Miller in Microporuous Materials, Vol. 2., (1994), 439-449. In the following examples the linear starting paraffin mixture may be the same as that used in the manufacture of conventional LAB. It is distilled to remove any boiling volatile material at approximately 40 ° C / 10 mmHg.

Step (a ii) Paraffin from step (a i) can be dehydrogenated using conventional methods. See, for example, US 5,012,021, 4/30/91 or US 3,562,797, 2/9/71. The suitable dehydrogenation catalyst is any of the catalysts described in US 3,274,287; 3,315,007; 3,315,008; 3,745,112; 4,430,517; and 3,562,797. For the purposes of the present example, dehydrogenation is in accordance with US 3,562,797. The catalyst is zeolite A. The dehydrogenation is carried out in the vapor phase in the presence of oxygen (paraffin: 1: 1 molar dioxygen). The temperature is on the scale of 450 ° C-550 ° C. The ratio of grams of catalyst to total feed moles per hour is 3.9.

Step b): Alkylation of the product from step a) using an aromatic hydrocarbon To an autoclave glass liner is added one molar equivalent of the mixture of step a), 5 molar equivalents of benzene and 20% by weight, based on the olefin mixture, of a shape selective zeolite catalyst (acid mordenite catalyst Zeocat ™ FM-8 / 25H). The glass liner is sealed inside a stainless steel oscillating autoclave. The autoclave is purged twice with 17.58 kg / cm2 nanometer N2, and then loaded at 70.3 kg / cm2 nanometer N2. With mixing, the mixture is heated at 170-190 ° C overnight for 14-15 hours, after which time it is cooled and removed from the autoclave. The reaction mixture is filtered to remove the catalyst. Benzene and any unreacted paraffin are distilled and recirculated. A nearly colorless or colorless transparent liquid product is obtained.

Step c): Sulfonation of the product of step b) The modified alkylbenzene sulfonate mixture of step b) is sulfonated with sulfur trioxide / air without using any solvent. See US 3,427,342. The molar ratio of sulfur trioxide to alkylbenzene is from about 1.05: 1 to about 1.15: 1. The reaction stream is cooled and removed from the excess sulfur trioxide.

Step d): Neutralization of the product of step c) The product of step c) is neutralized with a slight excess of sodium hydroxide to give sodium salt of modified alkylbenzenesulfonate.

EXAMPLE 12 The procedure of example 1 is repeated using different aromatic hydrocarbons. In one test benzene is replaced by toluene. In a second test, a mixture of toluene (2%) and benzene (98%) is used.

EXAMPLE 13 Compositions for cleaning product In this example the following abbreviation is used for modified alkylbenzenesulfonate, sodium salt form or potassium salt form, prepared according to any of the above process examples: MAS The following abbreviations are used for auxiliary materials for cleaning products : APA: Amylolitic enzyme, 60KNU / g, NOVO, Termamyl® 60T C8-C10 amidopropyldimethylamine Bicarbonate Sodium bicarbonate, anhydrous, 400μm -1200μm Borax sodium tetrahydrate decahydrate Brightener 1 4,4'-Bis (2-sulphotrisyl) biphenyl Disodium Brightener 2 4,4'-Bis (4-anilino-6-morpholin-1,3,5-trizin-2-yl) amino) stilbene-2: 2'-disulfonate C45AS Alkylsulfate of C-? -C-? 5 linear, sodium salt CaC12 Calcium chloride Anhydrous Na2CO3 carbonate, 200μm - 900μm Cellulase Cellulolytic enzyme, 1000 CEVU / g, NOVO, Carezyme® Citrate trisodium citrate dihydrate, 86.4%, 425μm-850μm Citric acid Anhydrous citric acid CMC Sodium carboxymethylcellulose CxyAS C? X-C yy alkyl sulfate, sodium salt or other salt if CxyEZ is specified C? X-? And branched primary ethoxylated alcohol (z moles of average ethylene oxide) CxyEzS C? XC alkylcytoxy sulfate and salt sodium (z moles of average ethylene oxide, another salt if specified) CxyFA Fatty acid of C? xC-? and Diamine Alkyldiamine, eg, 1,3 propane diamine, Dytek EP, Dytek A, (Dupont) Dimethicone Mixture of 40 (gum) / 60 (fluid) by weight of SE-76 dimethicone rubber (GE Div. Silicones) / dimethicone fluid with a viscosity of 350 cS. DTPA Diethylenetriaminepentaacetic acid DTPMP Diethylenetriaminepenta (methylenephosphonate), Monsanto (Dequest 2060) Endolase Endoglucanase, activity 3000 CEVU / g, NOVO EtOH Ethanol Fatty acid (12/14) C12-C14 fatty acid Fatty acid (RPS) Rapeseed fatty acid Fatty acid (TPK) Palm seed fatty acid HEDP 1, 1-Hydroxydandiphosphonic acid Isofol 16 Guerbet alcohols of C16 ( average) (Condea) Linear Alkylbenzenesulfonate (C11.8, Na or K salt) Lipase Lipolytic Enzyme, 100kLU / g, NOVo, Lipolase® LMFAA C12-C14 alkyl-N-methylglucamide LMFAA C12-C14 alkyl-N-methylglucamide MA / AA Maleic / acrylic acid copolymer 1: 4, sodium salt, average molecular weight 70,000. MBAEx Middle branched chain primary alkyl ethoxylate (average total carbons = x; average EO = 8) MBAE? S2 Branched medium chain primary alkyl ethoxylate, sodium salt (average total carbons = z; average EO = x) MBASX Primary alkyl branched chain average, sodium salt (average total carbons = x) MEA Monoethanolamine MES Alkylmethyl ester, sodium salt MgCI2 Magnesium chloride MnCAT Catalyst of macrocyclic manganese bleach as in EP 544,440 A or, preferably, use [Mn (Bciclama) CI2] where Bciclama = 5,12-dimethyl-1, 5,8 , 12-tetraaza-bicyclo- [6.62] hexadecane or a tetra-aza macrocycle with comparable bridge. NaDDC Sodium dichloroisocyanurate NaOH Sodium hydroxide NaPS Paraffinsulfonate, sodium salt NaSKS-6 Crystalline layered silicate of formula d-Na2Si2O5 NaTS Sodium toluenesulfonate NOBS Nonanoyloxybenzenesulfonate, sodium salt LOBS C12 oxybenzenesulfonate, sodium salt PAA Polyacrylic acid (molecular weight = 4500) PAE Ethoxylated tetraethylenepentamine PAEC Dihexylenetriamine ethoxylated methyl quatemized PB1 Anhydrous sodium perborate of nominal formula NaBO2H2O2 PEG Polyethylene glycol (molecular weight = 4600) Percarbonate Sodium percarbonate, nominal formula 2 a2CO3.3H2O2 PG Propanediol Photoblancizer Sulfonated zinc phthalocyanine encapsulated in PIE dextrin soluble polymer Ethoxylated polyethyleneimine Protease Proteolytic enzyme 4KNPU / g, NOBO; Savinase® QAS R2.N + (CH3) x (C2H4O) and H) z with R2 = C8-C? 8 x + z = 3, x = 0 to 3, z = 0 to 3, y = 1 to 15. SAS Alkylsulfate secondary, sodium salt Silicate Amorphous sodium silicate (SiO2: Na2O, ratio 2.0) Silicone antifoam Polydimethylsiloxane foam controller plus siloxane-oxyalkylene copolymer as the dispersing agent; foam controller ratio: dispersion agent = 10: 1 to 100: 1 SRP1 Esters blocked at the ends with sulfobenzoyl with base structure oxyethyleneoxy and terephthaloyl SRP2 Ethoxylated and sulfonated terephthalate polymer SRP3 Ethoxylated terephthalate polymer and end blocked with methyl STPP Anhydrous sodium tripolyphosphate Sulfate Anhydrous sodium sulfate TAED Tetraacetylethylenediamine TFA Alkyl-N-methylglucamide from C16-18 Zeolite A Hydrated sodium aluminosilicate, Na12 (A102SiO2). 27H2O; 0.1 -10μm Zeolite MAP Zeolite detergent grade (aluminum P maximum) (Crosfield) The example is illustrative of the present invention, but is not intended to limit or otherwise define its scope. All parts, percentages and ratios used are expressed as percentage by weight, unless otherwise indicated. The following laundry detergent compositions A to E according to the invention were prepared: EXAMPLE 14 Compositions for cleaning product The following liquid laundry detergent compositions F to J were prepared according to the invention. The abbreviations are like

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for preparing a modified alkyl benzene sulphonate surfactant suitable for use in cleaning products, said method comprising: a) reducing the linearization of an olefin having a molecular weight of at least 126 and not more than 280 isomerizing skeletally, in presence of a restricted skeletal somerization catalyst, a substantially linear olefin preformed to have at least said molecular weight; and b) a monoalkylation step having an internal isomer selectivity of from about 0 to 40, which comprises reacting the product of step a) with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst .

2. A process for preparing a modified alkylbenzene sulfonate surfactant suitable for use in cleaning products, said process comprising: a) a step of arriving at a reduced linearization alkylating agent selected from an olefin having a molecular weight, n , of at least 126 and not more than 280 and produced by a sequence of steps comprising: (i) skeletally isomerizing a linear paraffin having a molecular weight of n + 2, wherein n is the mentioned molecular weight of said olefin; and (ii) dehydrogenating the isomerized paraffin and b) a monoalkylation step having an internal isomer selectivity of 0 to 40, which comprises reacting the product of step a) with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst.

3. A method according to any of claims 1 or 2, having the additional steps of: c) sulfonating the product of step b); and one or more steps selected from: d) neutralizing the product of step c) and e) mixing the product of step c) or d) with one or more auxiliary materials for cleaning products; thus forming a cleaning product.

4. A process according to any of claims 1 or 2, further characterized in that said alkylation catalyst of step b) is selected from alkylation catalysts containing form-selective acid zeolite.

5. A method according to claim 1, further characterized in that said restricted skeletal isomerization catalyst is selected from the group consisting of zeolites and aluminophosphates having one-dimensional pore structures with a pore size of 4.2 Angstrom to 7 Angstrom.

6. A process according to claim 2, further characterized in that the catalyst of step a) (i) is a skeletal somerization catalyst for paraffins selected from SAPO-11 and its derivatives and isotypes.

7. - A method according to claim 2, further characterized in that the catalyst of step b) consists essentially of dealuminated H-mordenite.

8. A method for improving the cleaning performance of a consumer cleaning product containing alkylarylsulfonate surfactant, said method comprising: a) at least one de-linearization step of an alkyrene of C-io-C-iß to at least a minimum degree of 0.1 methyl portions per molecule of said alkylarene, and a maximum degree of 1.25 methyl potions per molecule of said alkylarene, said step comprises at least one step of linearization reduction carried out before, in parallel with, or subsequent to, a step of copying portions of the alkyl precursor and aryl precursor of said alkylarene; b) at least one step of sulfonating the slightly branched alkylarene product of step a); and c) at least one step of formulating the slightly branched alkylarylsulfonate surfactant product of step b) in the form of acid or salt in a cleaning composition.

9. A method according to claim 8, further characterized in that step a) forms 2-phenyl isomers of said alkylarene to a degree of at least 60%.

10. A method according to claim 8, further characterized in that step a) includes the use of a fluoride-free dealuminated mordenite catalyst. SUMMARY OF THE INVENTION The present invention is within the field of processes for making alkylbenzene sulfonate surfactants; the procedures include a combination of two essential steps, deslinealization and alkylation; the selected de-linearization step introduces particular types of limited branching into an aliphatic hydrocarbon having ten or more, but not more than about 16 carbon atoms; the hydrocarbon includes olefin having a hydrocarbon chain length suitable for the manufacture of detergents, for example, C10-C14 or a corresponding paraffin; the essential second step is an alkylation step having an internal isomer selectivity of from 0 to no more than about 40, wherein the hydrocarbon is used to monoalkyl benzene catalytically with an alkylation catalyst; said alkylation catalysts preferably comprise a solid containing at least partially crystalline porous zeolite, the zeolite having a moderate acidity and intermediate pore size; preferred alkylation catalysts include certain non-fluorinated, acidic, at least partially dealuminated mordenites; the processes consist of sulfonating, neutralizing and incorporating the resulting modified alkyl benzene sulfonate surfactants into consumer products; The invention also relates to the products obtained by the processes, including modified surfactants and consumer cleansing products that contain them. JT / MG / cgm * abg * mvh * xal * jtc * aom * P00 / 64F