MXPA01002243A - Improved processes for making surfactants via adsorptive separation and products thereof - Google Patents

Abstract

Processes for making particularly branched, especially monomethyl-branched or nongeminal dimethyl-branched surfactants used in cleaning products;preferred processes comprising particular combinations of two or more adsorptive separation steps and, more preferably, particular OXO and/or alkylation steps;products of such processes, including certain modified primary OXO alcohols and/or alkylbenzenes, modified primary OXO alcohol-derived alkoxylated alcohols, alkylsulfates and/or alkoxysulfates;alkylbenzensulfonate surfactants, and consumer cleaning products, especially laundry detergents, containing them. Preferred processes herein more specifically use specific, unconventional sequences of sorptive separation steps to secure certain branched hydrocarbon fractions which are used in further process steps to make olefins useful in OXO processes or as alkylating agents for arenes or for other useful surfactant-making purposes. Surprisingly, such fractions can even be derived from effluents from current linear alkylbenzene manufacture.

Description

IMPROVED PROCEDURE FOR ELABORATING SURGICAL AGENTS THROUGH ADSORPTIVE SEPARATION AND PRODUCTS THEREOF FIELD OF THE INVENTION The present invention is in the field of processes for making surfactants useful in cleaning products. Preferred methods comprise particular combinations of steps adsorptive separation to separate certain hydrocarbons using specific media. Preferably these means include combinations of two or more particular adsorbent beds and two or more particular types of rotary valves, as well as specific types of porous adsorbents having pore sizes greater than those used in manufacturing Conventional linear alkyl benzene. Preferred methods also utilize particular alkylation steps having specific internal isomer selectivities, or particular OXO reaction steps. The invention is also in the field of products of such processes, including certain modified alkylbenzenes, of surfactants of modified alkylbenzenesulfonate, detergent alcohols and surfactants derivable therefrom and consumer cleansing products, especially laundry detergents, which contain them. Preferred methods herein use sequences not conventional adsorptive separation steps to secure certain fractions of branched hydrocarbons which are then used in further processing steps as alkylating agents for loam or other useful surfactant processing purposes, such as OXO reactions to form particular detergent alcohols, followed by alkoxylation, sulfation or the like. Surprisingly, such fractions can be obtained even from effluents from the current manufacture of linear alkylbenzene.

BACKGROUND OF THE INVENTION Historically, highly branched alkylbenzene sulfonate 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. There followed a long period of improvements in the manufacturing processes of alkylbenzene sulfonates, making them as linear as possible ("LAS"). The overwhelming part of a huge linear alkylbenzene sulfonate based surfactant manufacturing technique is aimed at this goal. Commercial processes for large scale alkylbenzene sulfonate currently in use in the United States are directed to linear alkylbenzene sulphonates. However, linear alkylbenzenesulfonates are not free from limitations; for example, these could be more desirable if they were improved in terms of cleaning properties in hard water. In the petroleum industry, various processes have recently been developed to produce, for example, low viscosity lubricating oil or high octane gasoline, which the inventors have now discovered that 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 of the current commercial processes 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 LAS-based surfactant technique focused on the elaboration of 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. Quite recently, it has been discovered that certain zeolite-based catalysts can be used for alkylation of benzene with olefins. Said process step has been described in the context of normally conventional processes for the manufacture of linear alkylbenzene sulphonates. For example, the DETAL® method of UOP uses a zeolite alkylation catalyst. It is believed that the DETAL® process and all other current commercial processes for making alkylbenzene sulfonate do not meet the requirements of mt ^^ M ^ ^ ^ selectivity towards the internal isomer of the preferred process of the invention and of the alkylation catalyst defined hereinafter. Furthermore, 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 preferred 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 required by the present invention. Furthermore, in view of the desired linear character in the The alkylbenzene sulfonate products of the conventionally known processes, these generally also include steps directed towards the provision or processing of a substantially linear hydrocarbon, not a de-linearized one, prior to the alkylation. Possible exceptions are found in US documents No. 5,026,933 and US No. 4,990,718. These and Other known processes have numerous disadvantages 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 olefin dimerization step, the presence of large volumes of distillation fractions. that would need to be discarded or find customers not from 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.

The production of linear alkylbenzenes using particular adsorptive separation methods is also known in the art. See patent of E.U.A. No. 2,985,589. However, such procedures as described to this day, do not provide branched alkylbenzene sulphonates. It is also known in the art to prepare long chain methyl paraffins for use as industrial solvents by methods that include the formation of clathrates with urea and separation on "molecular sieves". See Chemical Abstracts, 83: 100693 and JP 49046124 B4. This procedure rightly involves double adduction with urea, treating for example a fraction of oil with urea once to remove the n-alkanes as complexes, and then a second time with excess urea to obtain mixed n-alkane adducts and monomethyl- long chain paraffins. Although this method may have some limited utility and may be included in the general methods of the invention as defined more broadly, its limitations are considerable. It is not known that this process, although dating from 1974, has been incorporated into any general procedure for preparing surfactants such as the modified alkylbenzene sulphonates described herein. As described in the following prior art section, it is also known how to make various OXO alcohols and make surfactants from them. However, currently available OXO alcohols have disadvantages, such as in the production of surfactants that are less soluble at a given chain length than would be desired for low wash temperatures that are increasingly popular or that rely on relatively expensive 5 such as olefin oligomerization, isomerization and disproportionation; or that still have a relatively high content of linear material.

TECHNICAL BACKGROUND WO 97/39090, WO 97/39087, WO 97/39088, WO 97/39091, WO 98/23712, WO 97/38972, WO 97/39089, US 2,985,589; Chemical Abstracts, 83: 100693; JP 49046124 B4 07/12/74; EP 803,561 A2 10/29/97, EP 559,510 A 9/8/93; EP 559,510 B1 1/24/96; US 5,026,933; US 4,990,718; US 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; SU 793,972, 1/7/81; US 2,564,072; US 3,196,174; US 3,238,249; US 3,355,484; US 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; US 5,196,625; EP 364,012 B, 2/15/90; US 3,312,745; US 3,341, 614; US 3,442,965; US 3,674,885; US 4,447,664; US 4,533,651; US 4,587,374; US 4,996,386; US 5,210,060; US 5,510,306; WO 95/17961, 7/6/95; WO 95/18084; US 5,510,306; US 5,087,788; US 4,301, 316; US 4,301, 317; US 4,855,527; US 4,870,038; US 5,026,933; US 5,625,105 and US 4,973,788 are useful as background for the invention. The ^^^^ EP 559,510 A and B cited in particular refer to the production of high octane gasoline recirculating flows to a reactor for isomerization. The grafted porous materials of EP 559,510 and the grafting of zeolites, for example, by tin alkyls, are useful in the present invention. Similarly, US 5,107,052 relates to the improvement of octane grades of gasoline and describes the separation of C4-C6 methyl paraffins using various molecular sieves such as AIPO4-5, SSZ-24, MgAPO-5 and / o MAPSO-5 containing less than 2% water. These screens can selectively adsorb dimethylparaffins without adsorbing normal monomethylparaffins and paraffins. 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 references of literature. This work provides access to a large amount of literature describing various procedures and process steps such as dehydrogenation, alkylation, alkylbenzene distillation and the like. See also "Detergent Alkylate" in Encyclopedia of Chemical Processing and Design, McKetta and Cunningham eds., Marcel Dekker, N.Y., 1982, especially pages 266-284. Adsorption processes such as the Sorbex UOP process and other associated processes are also described in Kirk Othmer Encyclopedia of Chemical Technology, 4a. ed., Vol. 1, see "Adsorption and Liquid Separation", including pages 583-598 and references cited therein. See also UOP Corp. publications, including "Processing Guide" available from UOP Corp., Des 5 Plaines, Illinois. Commercial methods of isolation and purification of paraffins using molecular sieves include MOLEX® (UOP Inc.), a liquid phase process and ISOSIV® (Union Carbide Corp.) as well as ENSORB® (Exxon Corp.) and TSF® or the selective Texaco finishing procedure, which are vapor phase procedures. It is believed that all these procedures use 5 Angstrom molecular sieves as porous media. Where not indicated herein, the temperatures, pressures and other operating conditions and apparatuses for any process step are conventional, i.e., as they are already well known and as they are defined in the context of agent manufacturing. surfactants based on linear alkylbenzenesulfonate. The documents referred to herein are incorporated in their entirety. US 3,732,325, issued May 8, 1973, describes a process for the separation of aromatic hydrocarbons. 20 Documents US 3,455.8 5, issued July 15, 1969, US 3,291, 726, issued December 13, 1966, US 3,201, 491, issued August 17, 1965 and US 2,985,589, issued May 23, 1961, describe simulated moving bed sortiva separation processes ^ .M, r i,, - r i? I n - iftti _ ^^^^? Á ^^^^ ll? ^^^^^^^^^^^ m for hydrocarbons. The document 5,780,694, issued July 14, 1998 and WO 98/23566, published June 4, 1998, incorporated herein by reference, refer to certain branched detergent alcohols and surfactants derivable therefrom. These documents include a description of the well-known OXO process and of suitable catalysts for hydroformylation. Consult in particular columns 10 and 1 1 of '694. The 5,510,564 document, issued April 23, 1996, incorporated herein by reference, describes processes for purifying hydrocarbons, especially in the context of aromatics removal. Document 5,276,231, issued on January 4, 1994, describes removal of hydrocarbon aromatics by means of sulfolane extraction. US 4,184,943, issued January 22, 1980, discloses sorptive hydrocarbon separations. US 4,006,197, issued February 1, 1977, discloses sorptive hydrocarbon separations of n-paraffins. US 5,220,099, issued June 15, 1993, and US 5,171, 923, issued December 15, 1992, describes purification of paraffins by elimination of aromatics, sulfur, nitrogen and oxygen containing compounds, and colored bodies by magnesium sorption. innn i ".ifct ^^^^^ i Y or Na-X zeolite Surfactant Science Series, volume 7," Anionic Surfactants ", part I, Marcel Dekker, NY, Ed. W. Linfield, 1976, chapter 2" Petroleum - Based Raw Materials for Anionic Surfactants, pages 11-86, provides 5 general background information including for OXO processing (see page 71 et seq.) And for certain supply materials (see page 60 and following) To be considered, this reference under the heading "branched chain olefins" on page 65 et seq. does not disclose branched chain olefins suitable for use in the process of the present invention, the olefins identified as "branched chain" being of biologically "hard", unsuitable types. Discussion of the OXO procedure on page 72 and following shows the conversion of linear olefin to mixtures of aldehydes and / or "branched" and linear alcohols Again, this use of the term "branched" differs from the present In accordance with the invention, the present method involves all the use of at least partially branched methyl chain middle supply materials as the main source of branching, the OXO reactions herein provide specific methyl branched primary alcohols in which only secondary aspects of any branching are due to OXO reaction. Separately, the reference immediately above and the references cited therein also describe the UOP OLEX® process and useful sorbents therein, see for example pages 60- 63 referring to zeolites doped with Cu or Ag. See more in particular US 3,969,276, issued July 13, 1976 for type X- or Y- zeolites doped with silver. See also D.B.Broughton and R.C.Berg, Hidrocarbon Process, vol. 48 (6), 115 (1969); D.B.Broughton and R.C.Berg, National Petroleum Refiners Association, 1969 Annual Meeting, March 23, 1969, technical document AM-69-38; D.B.Broughton and R.C.Berg, Chemical Engineering, January 26, 1970, page 86, article entitled "Two process team up to make linear monoolefins". Encyclopedia of Chemical Technology by Kirk Othmers, 4th edition, vol. 1, pages 893-913 (1991), article entitled "Alcohols, Higher Aliphatic", sub heading "Synthetic Processes" describes an OXO reaction to form detergent alcohols, see especially "Modified Cobalt Catalyst, One-Step, Low Pressure Process", on pages 904-906. Note once again that the diagrams showing branched methyl alcohols, see for example page 904, are made exclusively from linear precursors and the OXO branching is in the 2- position (as in the reference identified above). See also Surfactant Science Series, volume 56, "Anionic Surfactants", Marcel Dekker, N.Y. Ed. W. Linfield, 1996, chapter 1"Raw Materials for Anionic Surfactant Synthesis", pages 1-142, incorporated by reference, for further description of common supply materials in detergent manufacture, for description of known procedures for sortiva separation and others, for description of alkylation of ^ * = ^^^^^ detergent, and for description of steps of OXO or hydroformylation procedure (see for example pp. 23-25). The OXO process literature also includes "New Syntheses with Carbon Monoxide", Ed. J. Falbe, Springer-Verlag, New York, 1980. The commercial practice for making detergent alcohols that differ from those accessible herein is currently understood to include the sequence: isolation of linear paraffins from kerosene by sortiva separation, dehydrogenation by the PACOL® process (or similar) to linear internal olefins, isolation of the olefin from paraffin by the OLEX® process (or similar), and OXO reaction in one of two ways, either by means of a conventional OXO catalyst to give a primary alcohol substituted by 2-alkyl, for example as in LIAL® alcohols of ENI, or by isomerization of the olefin to the terminal position followed by terminal OXO addition, as practiced by the Shell / Mitsubishi process. See also document WO 97/01521 Al, published on January 16, 1997 and 95 ZA-0005405, published on January 25, 1995. Also consult several technical brochures and publications of Sasol and / or Sastech of South Africa, especially in relation to OXO alcohols that are already known or available or that can be manufactured by the OXO procedure owner to those companies. 2 ^^^^^ g ^^^^^^^ r? Id ^^^^ _ ^ _ z! ^ Í? ^ _ S ^^ ySs2Si? ^ Z ^. ^ Yi-y.-sZ ^^^ ^^^^^ BRIEF DESCRIPTION OF THE DRAWINGS Figures 1-18 are schematic drawings of some methods in accordance with the invention. Figure 8 shows in more detail a configuration of two adsorptive separation units, each being individually of a type such as that found in the first two adsorptive separation steps of figure 1 and figure 2. Note that the interconnections of Figure 8 are like those shown in Figure 1, but are different from those shown in Figure 2. Solid lines are used for essential steps of the procedure and for procedural flows. The dotted lines identify the steps and flows that might be non-essential in the procedures as defined more broadly but which are present in various preferred embodiments of the procedure. The rounded rectangles identify the steps, steps or units of procedure. The numbered lines identify supply materials, flows and intermediate products of the procedure. "SOR" identifies an adsorptive separation step. "4/5" serves to indicate that the adsorptive separation utilizes small pore zeolite, especially 5A Ca zeolite, which is completely conventional in the manufacture of linear alkylbenzene. "5/7" serves to indicate that the adsorptive separation uses a porous material such as SAPO-11 or any equivalent porous material that has a capacity to adsorb - - ^ - ** "- - - ~ ^ * - A < - < ** ^^^^ * ^ J ^^ • monomethyl-branched paraffins and / or • branched monomethyl monoolefins and / or • paraffins with non-geminal dimethyl and / or • olefins with non-geminal dimethyl while at the same time reject hydrocarbons with geminal dimethyl, cyclic hydrocarbons (with rings of five, six or more members) or higher branched hydrocarbons, which may be aromatic or aliphatic. "dimethyl gemina!" as used herein means that there are two methyls attached to an internal carbon atom of a hydrocarbon, as in: Only the SOR 4/5 sortiva stage and / or the SOR 5/7 soriva stage herein are of the type used in the stage (a) of the modified alkylbenzene preparation or stage (A) of the OXO alcohol preparation. modified primary, as described hereinafter. The large pore porous materials herein should not adsorb such hydrocarbons. On the contrary, the following hydrocarbons must be adsorbed. These are examples of what is meant by the term hydrocarbons with "dimethyl non-gemin!": Note that any of the methyl portions at the ends of the main chain are not taken into account to define the term "dimethyl geminate as used herein." In addition, consistent with In this convention, the following hydrocarbon must be adsorbed by the porous large pore material. This is a "monomethyl" hydrocarbon: The porous large pore materials suitable for use herein are described more generally and more fully in the following specification. "DEH" identifies a step of at least partial dehydrogenation of a flow (partial dehydrogenation being typical in the conventional manufacture of linear alkylbenzene although it can also be to use full dehydrogenation here) and "ALK" identifies an alkylation step. Any step, stage or unit identified with a rounded rectangle can in practice consist only of the essential step or can, more typically, include within it an additional step or steps They can be optional in the invention as defined more broadly, or which may be essential only in a preferred embodiment. Such additional steps not shown include, for example, the distillation steps of the types commonly practiced in the technique. In figures 9-18, "DIST" where it is present identifies a distillation step, "SOR O / P" where it is present identifies a sortiva separation step of olefin / parafma, for example the OLEX® procedure of UOP as used in stage (C) of the modified primary OXO alcohol which is described in detail below and "OXO" where it is present identifies a hydroformylation process step. Said process steps are well known in the art: see the "Background Art" section. Considering the aforementioned conventions, will note that Figure 1 illustrates a process having, sequentially, two adsorptive separations, collectively in accordance with the adsorptive separation step (a) of the invention as hereinafter defined; followed by a dehydrogenation step (step (b) hereafter); followed optionally by a step of alkylation (step (c) hereafter). Although step (c) is optional in the invention as defined more broadly, it is present in all preferred embodiments, which relate to the manufacture of modified alkylbenzenes according to the invention and, when g | ^ jfcg manufacture surfactants based on modified alkylbenzenesulfonate, typically followed by (d) sulfonation, (e) neutralization and (f) mixed to formulate it as a consumer cleansing product. Steps (d) through (f) use conventional means and are not explicitly shown in Figures 1-8. In the procedure of Figure 1, a hydrocarbon-based feedstock is passed to the first adsorptive separation step, for example a step in accordance with US 2,985,589, which uses a zeolite bed of 4-5 Angstroms . A flow of linear hydrocarbons is discarded as a flow of reject material 6. For comparison, in conventional manufacture of linear alkylbenzene, flow 6, consisting of a high proportion of linear hydrocarbons, would pass to DEH while step SOR 5 / 7 and the associated flows would be absent. In the present process according to Figure 1, an intermediate flow of branched enriched hydrocarbon is retained and passed to a second adsorptive separation. The second adsorptive separation uses a particular type of porous medium and produces a branched enriched flow 3 (product of step (a) as defined below) which passes to the dehydrogenation reactor (DEH); as well as a flow of reject material 7. The particular type of porous medium is preferably a "large pore" zeolite, said zeolite is characterized herein by a larger pore size than that of the zeolites used in manufacturing of linear alkylbenzenes, and more preferably, a pore size above about 5 Angstroms to about 7 Angstroms although materials with larger pores can be used and their pore sizes can be "tuned" using, for example, tin alkyls. The flow 4 represents dehydrogenated hydrocarbon rich in branched compounds; flow 8 represents recycled branched paraffins. Also shown is an alkylation step according to the invention which is included in a preferred embodiment of the invention. The product from the alkylation step is a modified alkylbenzene as defined elsewhere herein. Figure 2 is a schematic drawing identifying the steps in another embodiment of the present method. Although generally similar to the procedure of Figure 1, the procedure of Figure 2 has important differences, especially in that the adsorptive separation steps are reversed with respect to the pore sizes in the beds adsorbents. Figure 4 is a schematic drawing identifying an embodiment of the invention which starts with a hydrocarbon-based supply material 23 such as a branched effluent from a conventional linear alkylbenzene manufacturing process, or from a conventional linear detergent alcohol procedure. An adsorptive separation step using particular porous media is used to produce a flow of reject material 27 and a ramified enriched flow 24. The latter is dehydrogenated in the labeled step. "m" -i as DEH The particular type of porous medium is preferably a zeolite having a pore size larger than that of the zeolites used in the manufacture of linear alkylbenzenes, and most preferably has a pore size above about 5 Angstroms to about 5 Angstroms. The dehydrogenated hydrocarbon-based stream 25 passes to an ALK alkylation step from which a modified alkylbenzene product 26 passes. An optional recycle stream is identified as 28. Figure 3 is a schematic drawing identifying one modality of the invention similar to that of figure 4 but using substantially different intermediate process material and supply compositions. For example, Figure 3 can use as feedstock 17 a C10-C14 paraffin fraction having the intrinsic linear / branched paraffin ratio as received, and from the Which are removed, the cyclic, aromatic hydrocarbons, branched with geminal dimethyl, branched with ethyl or with substituents greater than ethyl, as part of the process of the present invention. When comparing figure 3 and figure 4, it might seem in view of the apparently identical step configuration that The procedures illustrated therein are identical. This is not the case in view of the very different results achieved as a result of changing the hydrocarbon-based feedstock. Figure 4 uses as a feed material based on hydrocarbon 23 an effluent stream from a linear alkylbenzene manufacturing facility and produces a modified alkylbenzene 26 which is predominantly branched. The process of Figure 4 could be constructed as an "add-on" to a normal linear alkyl benzene manufacturing plant. In contrast, Figure 3 uses as a hydrocarbon-based feedstock a mixture of linear and branched paraffins of the type present intrinsically in, say, a jet / diesel fraction derived from kerosene, which has not been processed in a facility. of manufacture of linear alkylbenzene. The process of Figure 3 produces a modified alkylbenzene containing a mixture of methyl branched alkylbenzenes (non-conventional, in accordance with the invention) and linear (conventional) alkylbenzenes. The procedure of Figure 3 can be constructed as a "stand-alone" installation that does not need to be connected to a conventional manufacturing facility. linear alkylbenzene. It is intended that these observations better illustrate the process of the present invention and should not be taken as limitations. Figure 5, Figure 6 and Figure 7 are schematic drawings identifying additional embodiments of the invention to accommodate other different hydrocarbon-based feedstocks. More specifically, these figures illustrate methods that accommodate mixed paraffin / olefin-based feedstocks. Figure 8 shows in more detail the particular configuration of the adsorptive separations which are found in other process illustrations, for example in Figure 1 and Figure 6. Each block represents an adsorptive separation unit. Within each block, a vertical arrangement of adsorptive separation beds (AC to the left of each block) is controlled by a rotary valve (RV). The adsorptive separation is accompanied by distillations in the RC and EC columns. The flows marked "Feeding Material", "Extract" and "Refined" on the leftmost side of the adsorptive separation correspond to the flows marked "1", "6" and "2" in Figure 1. The flow of refined material from the first adsorptive separation (and not the extract as would be the case in the conventional manufacture of linear alkylbenzene) becomes the feedstock for the second adsorptive separation. The refined material of the second adsorptive separation in Figure 8 corresponds to the flow 7 in Figure 1. The extract of the second adsorptive separation in Figure 8 corresponds to the flow 3 in Figure 1: this is the flow that in the present process is dehydrogenated and / or alkylated. Figure 8, as indicated, also serves to illustrate in greater detail the individual adsorptive separations herein. Therefore, although the connections are not as shown in Figures 2, 3, 4, 5 and 7, any individual adsorptive separation of Figures 2, 3, 4, 5 and 7 can be represented in greater detail using an interconnection appropriate to the detailed units illustrated in any of the blocks in Figure 8. The convention is used in Figures 1-7 to describe fractions of adsorbed hydrocarbons by the porous media as they exit above the adsorptive separations marked "SOR" while the non-adsorbed fractions are shown as coming out below the adsorptive separations marked "SOR". The "above" fraction 5 is sometimes referred to in the art as an "adsorbate" or "extract" and the "below" fraction is sometimes referred to as a "refinement" or "effluent". The "above" and "below" conventions used herein are designed to make reading of the procedure figures more convenient and should not be to consider as a limitation of the practical executions of the method of the invention to any particular geometric arrangement. Using principles similar to those used in Figures 1-8, Figure 9 illustrates a process for the production of modified primary OXO alcohols using medium chain internal olefins.

Branched methyl having carbon numbers suitable for detergent application as intermediates and in which the OXO catalyst pre-isomerizes the internal olefin for a long time to an alpha olefin and then hydroformylates predominantly at the terminal carbon atom. In more detail, the hydrocarbon feed material 51 is distilled using DIST distillation column to ensure a suitable hydrocarbon feedstock for the remaining part of the process. The feedstock 1 may desirably be a portion of narrow carbon scale paraffin. You also get a light distillation portion 52 and a heavy distillation portion 53, but are not used additionally to make the OXO alcohols herein. The hydrocarbon feed material is passed through a simulated movable bed sortiva separation system comprising SOR 4/5 units followed by SOR 5/7, each suitably of the MOLEX® type, connected in the order that it shows. The configuration is established in such a way that a linear flow enriched (an adsorbate) rich in linear paraffin and identified as 6 in Figure 9 is rejected from the SOR 4/5 unit. An intermediate-branched enriched flow (a raffinate) 2, which is enriched in branched methyl paraffins, proceeds to the SOR 5/7 unit. The rejection flow 7 of SOR 5/7 containing cyclic, aromatic, branched ethyl and branched paraffins with higher substituents is discarded. The enriched-branched flow 3 from SOR 5/7 now a flow of methyl branched purified paraffin, proceeds to the DEH dehydrogenator, for example of the PACOL® type where up to 20% of it is converted predominantly to the corresponding mono olefins . The enriched branched flow 4 (olefinic), which contains said mono olefins together with unreacted paraffins and some diolefin impurities, proceeds to SOP O / P, which is an adsorptive separation system of simulated movable bed configured to use OLEX® methods or similar for the separation of paraffin olefins. Suitably, for example, I adsorbent is copper or silver on X or Y zeolites. From SOR O / P, a branched-enriched, purified olefinic flux (adsorbate) 55, now mainly branched methyl olefins, proceed to an OXO reactor. The recycle stream 8 is predominantly branched methyl paraffins. The OXO reactor is configured for what is known in the art as a "one-step, low pressure OXO process", using a catalytic metal other than iron, said metal being modified with bulky phosphine ligands (see reference in Background) . The raw modified primary OXO alcohol, product stream 58, is separated from the recyclable material using distillation and other auxiliary means that are not shown and the clean modified primary OXO alcohol, now released from recyclable material, emerges as the 57th stream. picture below for more detailed description of the composition of each flow. Figure 10 is similar to Figure 9 with the exception that it incorporates one or more treatment steps after the dehydrogenation step, to hydrogenate diolefin impurity produced in the dehydrogenator and convert it back to mono-olefin. This is typically a DEFINE® type stage from which a UOP Corp. license may be obtained. Additionally, one or more additional steps of aromatics removal may be present, for example the PEP® UOP process, primarily to remove aromatic impurities formed during the dehydrogenation. Figure 11 is similar to Figure 10 except that it is simplified in that it uses an olefin / paraffin mixture as feed material to the OXO reactor and that the recycle stream 8 is now a > . . *. Mw, -. *. ^ ¡Zz = «and large fraction (> 70%) of the material produced in the OXO reactor. Figure 12 is similar to Figure 10 except that the SOR 4/5 and SOR 5/7 units have a reverse configuration. Figure 13 is similar to Figure 11 except that the SOR 4/5 and SOR 5/7 units have a reverse configuration. Figure 14 is similar to Figure 12 except that SOR 4/5 is removed in such a manner that a mixture of linear and branched methyl compounds proceeds through the process. The final product is a branched methyl primary mixed linear OXO alcohol. Figure 15 is similar to Figure 13 except that SOR 4/5 is removed in such a manner that a mixture of linear and branched methyl compounds proceeds through the process. The final product is a branched methyl primary mixed linear OXO alcohol. Figure 16 is similar to Figure 10 except that the plant is equipped such that the methyl branched olefinic flow 55 can be used to make modified alkylbenzene and / or modified primary OXO alcohols. Figure 17 is similar to Figure 11 except that the plant is equipped so that the branched methyl olefin flow 54 can be used to make modified alkylbenzene and / or modified primary OXO alcohols. Figure 18 is similar to Figure 14 except that the plant is equipped so that the methyl branched linear olefin flow 61 is The product can be used to manufacture a product comprising modified alkylbenzene and / or modified primary OXO alcohols together with the corresponding linear counterparts.

BRIEF DESCRIPTION OF THE INVENTION In a preferred embodiment, this invention relates to a process for preparing modified alkylbenzene sulfonate surfactants or modified primary OXO alcohols and surfactants derivable therefrom, or even combinations of these types of different surfactants. The process starts from hydrocarbon-based feedstocks that are defined in more detail elsewhere herein. "Modified" means a very particular type of branching. Specifically, for example, in the context of the OXO alcohols of the present, "modified" means that there is a branching with methyl at different positions to the usual OXO position, while substantially avoiding ramifications at positions or types that would affect in an adverse way the biodegradation. Preferably, "modified" refers to substitution in position of the middle part of the chain, mono-lower alkyl, especially monomethyl substitution of the OXO alcohol. The process comprises (a) a particularly defined adsorptive separation step and, when making modified alkylbenzenes and / or alkylbenzene sulfonates, (c) a step of b * S * .- * zyz.-y ^ alkylation. Of significant utility to the detergent manufacturer, the hydrocarbon-based feedstock can be a refining or adsorptive separation effluent that is obtained from a linear alkylbenzene manufacturing process, or from conventional linear detergent alcohol processes, although other feedstocks may be used, such as jet / diesel or olefins. When the feedstock is paraffinic, the process modalities typically, and preferably, include (b) a dehydrogenation step inserted in the sequence between the separation adsorptive and alkylation and, when a modified alkylbenzene is the desired product, (c) an alkylation step. When the feedstock is olefin, obviously, dehydrogenation is not essential. In general, the alkylation step is preferably followed by (d) sulfonation; (e) neutralization; and (f) formulation as cleaning products for the consumer by mixing, agglomeration, compaction, spray drying and the like. Any of the stages can have more than one step and include options such as distillation, with the condition that it includes at least the specified minimum. When a modified alkylbenzene is manufactured, step (a), The adsorptive separation comprises at least partially separating the hydrocarbon-based feedstock that is selected from olefinic feedstocks, paraffinic feedstocks and mixed olefinic / paraffinic feedstocks, at least It is a flow enriched with branched compounds comprising an increased proportion (for example, in relative terms at least greater than 50%, and in absolute terms, that is to say in terms of weight percent, at least about 10% by weight) of branched non-cyclic hydrocarbons in relation to said hydrocarbon-based feedstock and typically, one or more additional streams, for example at least one flow enriched with linear compounds comprising an increased proportion (for example, in relative terms at least greater than 50%, and in absolute terms at least about 10% by weight) of linear non-cyclic aliphatic hydrocarbons in relation to said material hydrocarbon-based feed. Other flows present in the process may vary in composition. Such flows include reject material flows, in which undesirable cyclic and / or aromatic components from the feedstocks are present at levels generally exceeding those of the feedstock; Recirculation flows and the like may also be present. In greater detail, the adsorptive separation part, (a), of the process has one or more steps comprising, first, supplying the hydrocarbon-based feedstock, then at least one step selected from the adsorptive separation using means porous (preferred), clathrate formation using a clathrate-forming compound that is selected from urea, thiourea and from alternative clamp forming amides; and combinations thereof. This stage uses ¡^^ adsorptive separation media with simulated motion bed known from the art (see in particular US Pat. No. 2,985,589 incorporated herein in its entirety) comprising both of at least one bed having said porous media or said clathrin forming compound (see for example US Pat. No. 2,985,589, FIG. 1 and the associated description) and a device, typically a rotating valve of highly specialized design, to simulate the movement of said porous media or said clathrate forming compound in counter-current to a hydrocarbon flow in said bed. (See in particular US Pat. No. 2,985,589, FIG. 2). Particularly unusual and novel in the context of the present process is that, at least, the adsorptive separation with simulated movement bed in the present invention is used to extract an essential flux rich in branched compounds, ie, exactly the opposite of practice. used in the manufacture of linear alkylbenzenesulfonate-based surfactant. This essential difference is also associated with having a different content of the bed compared to conventional practice, ie there is at least one bed containing porous media which differ from the 4-5 Angstroms zeolites normally used for the manufacture of linear alkylbenzene by having larger pore size and by reconfiguring the process equipment, notably said bed and said device, so that these are connected differently with the associated process steps. More specifically, these ^^ m ^^^^ ^ fe ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ fc ^^^^^^ ^^^^^^ g ^^ means are configured in such a way that the flow of branched compounds is passed through the process, while, however, any of the fluxes rich in linear compounds useful for other purposes, or are rejected of the process of the present invention or are present accompanying flows rich in branched compounds. further, step (a) of the process of the present (or step (A), when producing branched primary OXO alcohols) suitably comprises the use of at least one porous medium which is selected from the group consisting of porous media having a minimum pore size at least larger than the pore size required for the selective adsorption of linear non-cyclic hydrocarbons, said pore size being no greater than about 20 Angstroms, preferably not greater than about 10 Angstroms. When said hydrocarbon-based feedstock comprises more than about 10% paraffins and invariably with higher levels, for example 11% to 90% or more of paraffins, the present process preferably includes an additional step, (b), of at least partial dehydrogenation of said flow enriched with branched compounds. The dehydrogenation can be done using catalysts and known conditions. When modified alkylbenzenes are manufactured, without considering the type of feedstock, the process of the present invention preferably comprises (c) reacting an enriched flux with - * ----- - üA * ^ ¡^ ^ | ^ g branched compounds prepared by one or both of the preceding steps (adsorptive separation with dehydrogenation) with the proviso that the flow enriched with branched compounds finally contains olefin , typically at least about 5%, more typically at least about 15% olefins, generally 5% to 90% or more) with an aromatic hydrocarbon that is selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst. The preferred alkylation step herein has a low selectivity to the internal isomer from 0 to not more than about 40, preferably not more than about 20, and is described and more fully defined elsewhere herein. It is believed that such alkylations with low alkylation selectivity are novel in their own right in the context of the manufacture of modified alkylbenzene. Preferred methods herein in addition preferably fulfill at least one, and most preferred both, of the following requirements: as a first requirement, said means of step (a) comprise one, two or more of said devices and therefore minus two of said beds, comprising at least one of said porous middle beds differentiated relative to the contents of the other of said beds 20 by an increased capacity to retain non-cyclic aliphatic hydrocarbons branched with methyl. For example, zeolites having pore sizes above about 5 to not more than about 7 Angstroms are especially preferred. As the second requirement, «* ^ .- * ~~ -. I-A- ^ - * --- - -, ^ * ~ - * mm¡ * ^? Mtf * < When the modified alkylbenzenes are manufactured, said step (c) has a selectivity to the internal isomer from 0 to no more than about 40, preferably less as hereinafter defined. Preferred processes herein work in a manner contrary to and inconsistent with conventional practice for manufacturing alkylbenzene sulfonate based surfactants, which accepts linear materials for further processing and rejects most branched materials. Furthermore, in order to achieve this investment, it is necessary to use an unconventional interconnection of adsorptive separation operations as described and illustrated in the figures of this specification. Also in the preferred methods herein, said motion bed separation means simulated in said step (a) comprises not one but two of said devices. The number of devices taken in conjunction with its configuration is of particular importance to achieve the manufacture of the preferred compositions of the invention and increase the specific types of branching in the hydrocarbon-based streams. In addition, in certain preferred methods having two of Said beds, each comprising a different element of said porous means, each of said beds being controlled by one of said devices, and each of said devices having a minimum of eight ports (as defined in the US document). 2,985, 589) to achieve simulated movement of said porous media in said beds In addition, each of said beds was preferably divided into a vertically arranged array of at least eight sub-beds (see Figure 1 in US 2,985,589). Preferably, stage (a) uses exclusively porous media, instead of clathrate-forming compounds, in said beds.The methods of the present when modified alkylbenzenes are manufactured, may have one or more steps after the alkylation step. they may include the additional step of (d) sulphonating the product of step (c) .Sulfonation may be followed by the additional step of (e) neutralizing the product of step (d) .Such steps may be followed by (f) mix the product from step (d) or (e) with one or more accessory materials for cleaning product; thus forming a cleaning product. The present invention also encompasses modified alkylbenzene produced by any of the methods herein; as well as modified alkylbenzenesulfonic acid or modified alkyl benzene sulphonate based surfactant in any known salt form such as the sodium salt form, the potassium salt form, the salt form Ammonium, the substituted ammonium salt form or the like, produced by any of the methods herein; as well as consumer cleaning products produced by any of the methods herein.

• "Hir- '- *' f -? -__ ¡__j ^ j2¿ 2j¡j¡ £ ^ _¡¡¡¡ ^^^^^^^^ Likewise, when anionic surfactants are produced From the modified primary OXO alcohols as taught herein, all forms of salts identified above of the surfactants are encompassed by the invention The cleaning product embodiments herein, whether incorporating the modified alkylbenzene sulfonates and or any of the surfactants derived from modified primary OXO alcohols taught herein, include laundry detergents, dishwashing detergents, hard surface cleaners and the like In such embodiments, the content of modified surfactants produced by the method of the present is from about 0.0001% to about 99.9%, typically from about 1% to about 50%, and the composition further comprises from about 0.1% to about 99.9%, typically from about 1% to about 90%, of adjunct materials for cleaning products such as surfactant coagents, detergency builders, enzymes, bleaches, promoters, activators or bleach catalysts and the like. The present invention also has alternative embodiments utilizing paraffinic hydrocarbon feedstocks, in which two adsorptive separations, particularly configured in almost the same manner as step (a) described herein for the production of modified alkylbenzene, are followed by additional steps other than ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^^^^^^^^^^^^^^ b benzene alkylation step (c), and leading to useful cleansing surfactants. Such steps replacing the alkylation step (c) may include at least one step that is selected from: dehydrogenation, chlorination, sulfoxidation, oxidation to a C8-C20 alcohol and oxidation to a C8-C20 carboxylic acid or salt of the same; optionally followed by a step of: glucosamidation, conversion to an amide-based surfactant not derived from saccharide (eg, a monoethanolamide-based surfactant or any such amides that do not have a glucose portion) and sulfonation as an ester . Other alternative modalities use a hydrocarbon-based feedstock containing 20% or more of branched olefins with methyl; again, this process has the adsorptive separations of step (a) particularly configured. The subsequent steps may include alkylation with benzene or toluene optionally followed by sulfonation; alkylation with phenol followed by at least one step of alkoxylation, sulphation, sulfonation or combinations thereof; hydroformylation to the alcohol optionally followed by at least one step of alkoxylation, glycosylation, sulfation, phosphating or combinations thereof; sulfonation; epoxidation; Bromhydration followed by amination and oxidation until the amine oxide; and phosphonation. The invention also encompasses the surfactants produced by such processes and the cleaning products produced by such processes. In addition, the present invention a ^ a.i "& zi includes especially useful embodiments in which the adsorptive separations of step (a) comprise at least one separation step using a grafted mordenite with organometallic compound such as a grafted mordenite with tin. The invention also encompasses a method comprising the use of a grafted mordenite for manufacturing detergent surfactants and any of the corresponding surfactants and consumer products produced using these specific porous media in any of the procedures defined above. The present invention has many other modalities and ramifications. In this way the present invention encompasses a process comprising: (A) a step of at least partial separation of a hydrocarbon-based feedstock comprising branched aliphatic hydrocarbons, more particularly, paraffinic hydrocarbons, having from 8 to 20 carbon atoms, in at least one flow enriched with branched compounds comprising an increased proportion of branched non-cyclic hydrocarbons in relation to said hydrocarbon-based feedstock and, optionally, , one or more of: B a flux enriched with linear compounds comprising an increased amount of linear aliphatic hydrocarbons in relation to said hydrocarbon-based feedstock; Ygg. & ^ 5 > A rejection material stream comprising cyclic and / or aromatic and / or branched hydrocarbons of ethyl or higher compound; wherein said step (A) comprises: - providing said hydrocarbon-based feedstock; and - adsorptive separation of said feedstock in said flows using porous media; said step (A) using adsorptive separation means of simulated movement bed comprises both of: - at least one bed containing said porous medium; and a device for simulating movement of said porous medium in a direction opposite to a flow of hydrocarbons in said bed; followed by additional stages (B), (C) and (D) (any of which may having one or more steps) as follows: (B) (i) at least partially dehydrogenate the enriched flux with branched compounds from step (A) thereby forming an olefinic flux rich in branched compounds comprising mono-olefin (optionally , large proportions may also be present, to 80% or higher, of paraffins together with impurities such as diolefins and / or aromatic impurities), optionally followed by one or more of (i) treating said olefinic flow rich in branched compounds to decrease the content therein of aromatic impurities; (C) optionally, i? - - • - "- ?? - - ~ 'and' ~ - * - ^ yy - ^^ - * '^ - ^ ----- - - ^^ t ?? tta t? ^ I tutb? aa? ii? m to at least partially concentrate said mono-olefins in the olefinic flow rich in branched compounds of step (B) by means of adsorptive separation using a solvent or known porous medium with the proviso that said solvent or porous medium are not identical to the porous medium of step (A) and are adapted for olefin / paraffin separations (as is the case, for example, for zeolite X or Y treated with copper or treated with silver), and, optionally, recycle paraffins concurrently to said dehydrogenation step (B), and (D) react said olefinic flow rich in branched compounds produced in step (B) or, optionally, as it is further concentrated in the stage (C), with carbon monoxide and hydrogen in the presence of an OXO catalyst, thus forming a modified primary OXO alcohol. of the present, the term "stage" refers to a collectively identifiable group of one or more procedural steps. For example, (A) is an adsorptive separation stage, essentially a modified MOLEX® stage from which one can obtain a license from UOP Corp., configured here in an unconventional way to enrich (instead of decrease as in practice) common) the branched content of hydrocarbons. Optional steps may be included as part of the same step such as distillation, addition or removal steps with boiling hydrocarbons 7.A ^ t ^ - - "^ - ^ ^^? ^^ l ^^^^ l ^^ me lower to wash adsorbent, etc., as is well known in the art. (B) is a dehydrogenation step, comprising at least one step of dehydrogenation but often including other optional steps such as those mentioned above in a specific manner For the essential processing technology for (B) a license can be obtained from UOP Corp., for example as the PACOL® process. (C) is essentially a conventional OLEX® step, again available from UOP Corp. (D) is preferably an OXO step of the type referred to in the art as a "low OXO". one-step pressure "and is well known in the technique. As with the other steps of this procedure, step (D) can be supplemented by other optional steps, for example, catalyst removal, etc. Unless stated otherwise, the convention herein will be to use capital letters (A, B, C) when reference is made to stages of the present procedure modality in which the The process includes making a modified primary OXO alcohol. The surfactants that can be derived from these new modified primary OXO alcohols and the alkylbenzenes mentioned above have significant advantages, such as being more soluble at a given chain length / carbon number which is important in view of the increasing popularity of low wash temperatures; and for having unexpectedly high dissolution rates when incorporated in detergent granules. In this way the OXO alcohols and the alkylbenzenes themselves have exceptional utility for the manufacturer ^ "^ J * ^ -jt- of cleaning compositions such as detergents for laundry heavy work, liquid dishwashing and the like. All percentages, ratios and proportions herein are by weight, unless specified otherwise, all temperatures are in degrees Celsius (° C) unless otherwise specified, all documents cited are, in part relevant, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION In one embodiment, the present invention relates to a process for preparing a modified alkylbenzenesulfonate-based surfactant from a hydrocarbon-based supply material. The equivalent terms "feedstock" and / or "feedstock" are used in the present invention to identify any hydrocarbon useful as a starting material in the process herein. In contrast, the term "flow" is typically used to identify a hydrocarbon that has passed through at least one step of the process. The hydrocarbon-based feedstock generally contains useful proportions of non-cyclic aliphatic hydrocarbons, either olefinic or paraffinic, or may include mixtures of such olefins and paraffins. The untreated supply material typically also includes varying amounts of cyclic and / or aromatic impurities, such as which are found, for example, in lane * hydrocarbon fractions for kerosene, jet / diesel (medium distillation). In the supply material, olefins and paraffins are generally present in both branched and linear forms. In addition, in general, branched forms in the supply material may be undesirable or may be desirable for the purposes of the present invention. The purposes of the present invention for providing cleaning products differ considerably, for example, from the manufacture of gasoline in which a high degree of methyl polyamide hydrocarbons is desired to increase the octane. The present invention provides methods for separating the particularly desired forms of hydrocarbon-based feedstocks for cleaning product purposes, and for incorporating them as surfactants (especially certain modified alkylbenzenesulfonates and / or surfactants based on modified primary OXO alcohols). and as cleaning products and intermediates of surfactants useful for such products. The term "modified" as applied in connection with any product of the present process means that the product contains a very particular type of branching and surprisingly departs from the linear structure which is currently thought to be preferred and used for agents surfactants for cleaning products. The term "modified" is further used to differentiate the products herein from highly branched cleansing surfactant structures, ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ conventional, such as those found in tetrapropilen- benzenesulfonates and all other conventional branched structures such as structures "two-tailed" or "Guerbert" or aldol-derived branched structures -É¡. The hydrocarbon-based feedstocks herein may vary widely but typically include methyl branches such as monomethyl., dimethyl (including geminal dimethyl), trimethyl, polymethyl, ethyl, and higher alkyl branches. The hydrocarbon-based feedstocks may contain quaternary carbon atoms. However, the tolerance for quaternary carbon atoms in the feedstock is much higher when the present process includes an alkylation step as taught hereinbelow. Preferred feedstocks herein in embodiments of the invention having an OXO processing step and not having an alkylation step are essentially free of quaternary carbon atoms. The components desired for the purposes herein include monomethyl-branched, dimethyl-branched, other than those branched with geminal dimethyl, and to some degree, especially at carbon contents greater than about 20, some proportion of trimethyl-branched. The hydrocarbon-based feedstocks include useful ratios, for example 5% -40% or more, of non-cyclic hydrocarbons having in general from about 9 to about 20 carbon atoms. - »- - - * - - * - • - - m ^^^^^^^ ^^^^^^^^^^ carbon depending on the type of surfactant agent for cleaning product or use cleaning of the modified surfactant that is being produced. More preferred, when modified alkylbenzenes and modified alkylbenzene sulphonates are manufactured, the non-cyclic aliphatic hydrocarbons in the supply material contain from about 10 to about 16, preferably from about 11 to about 14, carbon atoms. The processes of the present invention comprise a particularly defined adsorptive separation step and, for the purposes of manufacturing alkylbenzenes and modified alkylbenzene sulphonates, an alkylation step is also essential. When the supply material is paraffinic, the process modalities typically and preferably also include a dehydrogenation step inserted in the sequence between the adsorptive separation and the alkylation, or, when making modified primary OXO alcohols, between the adsorptive separation of the type. which is referred to as SOR 4/5 or SOR 5/7 in the figures, and the procedure stage OXO. In general, the alkylation step or the OXO step can be followed by additional steps such as sulfonation, typically followed by neutralization and formulation as consumer cleaning products by mixing, agglomeration, compaction, spray drying and the like. Also in general, any of the stages can have more than one step with the condition that it includes at least the minimum of one step.

Step (a), adsorptive separation, comprises at least partially separating the hydrocarbon-based feedstock that is selected from olefinic feedstocks, paraffinic feedstocks and mixed olefinic / paraffinic feedstocks, into at least one flow enriched with branched compounds comprising an increased ratio (eg, in relative terms compared to the feed material of at least greater than 50%, preferably of at least approximately greater than 100%, typically triple, quadruple or more and in absolute terms, ie in terms of weight percent, of at least about 10% by weight, typically at least 20%, more preferred from 30% to about 90% or more) of non-cyclic hydrocarbons , branched (especially the desired types identified above, particularly branched paraffins with methyl or branched mono-olefins) with methyl) relative to said hydrocarbon-based feedstock and optionally, one or more of: a flux enriched with linear compounds comprising an increased ratio (eg, in relative terms of at least greater than 50%, preferably of at least about 100% higher, typically triple, four times or more and in absolute terms of at least about 10% by weight, typically at least 20%, more preferred from 30% to about 90 % or more) of linear non-cyclic aliphatic hydrocarbons relative to said hydrocarbon-based feedstock, and a stream of re-chalking material containing cyclic and / or aromatic hydrocarbons or other impurities such as hydrocarbons with geminal dimethyl, branched hydrocarbons with ethyl or hydrocarbons with superior branching. Other flows present elsewhere in the present process may vary in composition. Such flows include flows of reject material, in which undesirable cyclic and / or aromatic components are present from the feedstocks at levels generally exceeding those of the feedstock; flows for recirculation that have compositions that depend on the parts of the process they connect and the like. Known procedures can be used in the present invention, such as those of US 5,012,021 or US 4,520,214 both incorporated by reference, to convert impurities, such as certain diolefins, back into mono-olefins using a selective catalyst. Other methods that may optionally be incorporated herein to selectively remove aromatic by-products formed in the dehydrogenation of paraffin include those of US 5,300,715 and US 5,276,231 which involve the use of one or more aromatics removal zones and / or extractors of aromatic compounds which may include, for example, sulfolane and / or ethylenediamine. In more detail, the adsorptive separation step or part of the process that is used to enrich the content of branched hydrocarbons in the feedstock has one or more steps comprising at least one step that is selected to provide a feedstock to Suitable hydrocarbon base and at least one step selected from the adsorptive separation using porous media, formation of clathrates using a clathrate-forming compound selected from urea, thiourea, and from clastic forming amides.; and combinations thereof. Most preferred, when combinations are used, at least one step is an adsorptive separation employing porous media of the larger pore type more fully described later herein. Step (a) (or step (A) when modified primary OXO alcohols are made) uses adsorptive separation means with simulated movement bed known from the art (see in particular US 2,985,589 incorporated herein by reference). whole) comprising both of at least one bed having said porous medium or said clathrate-forming compound (cf.

, US Pat. No. 2,985,589, FIG. 1 and the associated description) and a device for simulating the movement of said porous medium or said clathrate-forming compound counter-current to a hydrocarbon flow in said bed. (See in particular document US 2,985,589, Figure 2 and the associated description, or the variants in current commercial use for the production of linear alkylbenzenesulfonates). The device in question is typically a highly specialized rotary valve. In general, types of such valves such as those used in the current manufacture of linear alkylbenzene can be used in the present invention. The - Oh. . ^ fe-, ^ * ~~ andfi - »- -tt ~ .: - ^. - - ^ aai ==.

Adsorptive separation conditions. Pressure, temperatures and times can be like those used in the technique. See, for example, US 2,985,589. What is particularly unusual and novel in the context of the present process is that, at least, the adsorptive separation with a simulated movement bed in the present is used to extract an essential flux rich in branched compounds, ie, exactly the opposite of the practice used in the manufacture of linear alkylbenzenesulfonate-based surfactant. This essential difference is also associated with the change in the bed content so that it contains porous media which differs from the 4-5 Angstroms zeolites normally used for the manufacture of linear alkylbenzene and by reconfiguring the processing equipment, notably said bed and said device, so that these are connected differently with the associated procedure steps. More specifically, these means are configured in such a way that the flow of branched compounds is passed through the process, while, however, any of the fluxes rich in linear compounds useful for other purposes, or are rejected from the process of the present or are present accompanying flows rich in branched compounds. When said hydrocarbon-based feedstock comprises less than about 5% olefins, the present process preferably includes a further step, (b), or step (B) when producing primate, oxidized OXO alcohols, dehydrogenating by the least partial of the product of stage (a). The dehydrogenation can be done using any known dehydrogenation catalyst, such as those of the UOP De-H series and which are also illustrated hereinafter. The dehydrogenation conditions are similar to those used in the current manufacture of linear alkylbenzene sulfonate. When modified alkylbenzenes are manufactured, without considering the type of supply material treated, the present preferred process comprises (c) reacting the product of step (a), or when step (b) is also present in the previous steps , the product of step (a) followed by step (b), with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst. The preferred alkylation step herein has a low selectivity to the internal isomer from 0 to about 40, preferably no more than about 20, more preferred no more than about 10, as described and more fully defined elsewhere in the I presented. It is believed that such selectivities towards the low internal isomer are novel in their own right. In one embodiment, the alkylation step of the present is run in the presence of an excess of paraffin, which is then recovered and recirculated to the dehydrogenator. In another embodiment, the alkylation step is run in the presence of 5x to 10X in excess of arene. Any combination of such modalities is possible.

* J8"* Note that when the final flow rich in branched compounds, that is, the product of etap, (a), has an appreciable content of olefin, for example, greater than about 5% olefins in total, this flow can proceed directly to the alkylation step (c), then the 5 recovered paraffins can be recirculated to a dehydrogenation reactor for at least partial conversion to olefin. See, for example, Figures 5, 6, 7. Of great importance for the present invention, the preferred methods herein additionally preferably meet at least one, and most preferably both, of the following requirements: as a first requirement , said means of step (a) (or, when modified primary OXO alcohols are manufactured, the means of step (A)) comprise one, two or more of said devices (for example the aforementioned rotary valves or any of the others equivalent means) and by At least two of said beds, comprising at least one of said porous middle beds differentiated relative to the contents of the other one of said beds by an increased capacity to retain non-cyclic aliphatic hydrocarbons branched with methyl. For example zeolites having pore size at least larger than the sizes used in the Conventional manufacture of linear alkylbenzene and up to about 20 Angstroms, preferably up to about 10 Angstroms, more preferred even up to about 7 Angstroms, or other porous media such as certain silicoaluminophosphates or materials of the MCM type of & * r * -á ** -'y - '?? _ jrtpr? tr' - "É * ÉI Mobil, are suitable in the present condition provided that the pore sizes are as indicated. porous materials having pore sizes above about 7 Angstroms are used, it is often desirable to "fine-tune" the pore openings, for example by grafting tin alkyls into the pore openings, see EP 559,510 A incorporated therein. whole by reference herein As the second requirement, when modified alkylbenzenes are manufactured, said step (c) has a selectivity to the internal isomer from 0 to not more than about 40, preferably lower, as indicated above and as further defined hereinbelow, In other preferred methods, at least one of said beds comprises conventional porous media for the manufacture of linear alkylbenzenes, said beds being connected to said pro yield in a manner consistent with the at least partial increase in the proportion of non-cyclic aliphatic hydrocarbons branched with methyl in the streams passing to step (c) of said proc and with the at least partial decrease in the proportion of hydrocarbons linear non-cyclic aliphatics passing to step (c) of said proc at least partially removing said linear non-cyclic aliphatic hydrocarbons as reject material flow in step (a). In other words, the preferred methods herein work in a manner opposite to and inconsistent with conventional practice for manufacturing alkylbenzene sulfonate based surfactants, which rejects the materials - -T - Ü.r i - piif - I I - - a-mi ^^ ll? ^ Mim ^ íal ^^^^^^^^^^^^? branched and accepts linear materials for additional procng. Furthermore, in order to achieve this investment, it is necry to use an unconventional interconnection of adsorptive separation operations as already briefly described and as further illustrated in the figures herein. Also of great importance, in the preferred methods herein, said adsorptive separation means with simulated movement bed in said step (a) (or step (A) when making modified primary OXO alcohols) comprise not one, but two of said devices, or an individual device capable of simulating the movement of said porous means in at least two independent beds. In other words, for all of the preferred methods herein, it will not be sufficient to use an individual device, for example a device as taught in US 2,985,589. The number of devices taken in conjunction with their configuration is of particular importance to achieve the manufacture of the preferred compositions of the invention. In this way, in a hypothetical situation not known in the art, an increasing purification of a linear hydrocarbon could be achieved by means of two devices and two beds connected in series. A highly linear adsorbate of the first stage could proceed to an entry of the second stage of the adsorptive separation procfor further purification. A configuration as such is outside the present invention due to its incorrect connection of the stages, which leads to the increase of the . -. -yy *. and-- ~ y .. ..y ~ .. ~. * -. and V, ». - ^ í ^ ^ ^^^^^^^^^^^^^^ ^. A ^, V,? »^^. linearity and purity of a hydrocarbon The processes of the present, as already indicated, involve passing flows of branched material through several steps or steps, which require a connection of the devices that is consistent with the objective. This increases the specific types of branching in the hydrocarbon-based streams herein. Also of great importance in the preferred methods herein, there are two such beds, each comprising a different member of said porous means, each of which is controlled by said beds by one of said devices, and each of said devices having a minimum of eight ports to achieve the simulated movement of said porous means in said beds. In addition, each of said beds is preferably divided into an array of at least eight sub-beds placed vertically. Also preferably, stage (a) uses exclusively porous media in said beds. Therefore, the invention can use conventional beds and devices of the general type described in US 2,985,589; but its number and connection in the present process is novel and unprecedented in the alkylbenzene sulfonate manufacturing plants. Also, to better illustrate what has already been described, in certain embodiments of the preferred methods herein, said flux enriched with linear compounds is present in step (a) and step (a) comprises: (ai) separation adsorptive of said material hydrocarbon-based feed in said flux enriched with linear compounds and in an intermediate flow rich in branched compounds and reject flux enriched with linear compounds for the essential purposes of said process, by means of one of said beds of simulated movement; followed by (ai) adsorptive separation of said intermediate flow rich in branched compounds in said flux enriched with branched compounds comprising an increased proportion of branched non-cyclic aliphatic hydrocarbons (more particularly branched with methyl) relative to said flux enriched with linear compounds , and a flow of reject material comprising at least an increased proportion of cyclic and / or aromatic hydrocarbons relative to said flow enriched with branched compounds, by means of the other of the simulated movement beds. Said reject material flow in step (a-ii) may further comprise undesired branched hydrocarbons which are selected from branched hydrocarbons with geminal dimethyl, branched hydrocarbons with ethyl and hydrocarbons with branching greater than that of ethyl; and wherein the non-cyclic aliphatic hydrocarbons of said intermediate flow rich in branched compounds and said flow enriched with branched compounds comprise a reduced proportion of said branched hydrocarbons with geminal dimethyl, branched hydrocarbons with ethyl and hydrocarbons with branching greater than that of ethyl with respect to to said hydrocarbon-based feedstock. In terms of tolerance of those various constituents] flux enriched with intermediate branched compounds, branched hydrocarbons with ethyl are much more acceptable than the geminal, cyclic and aromatic dimethyl components. In general, a minimum of "increasing proportion", "decreasing proportion" or "enrichment" of any of the components in any of the steps herein corresponds to any increase (enrichment) or decrease in the proportion useful to the purposes of the invention indicated in a practical manner. Such quantities are well illustrated through the specification. Further in said process, said flow compositions can be achieved by selecting as the porous media: a member that is selected from the group consisting of zeolites with pore size of 4-5 Angstroms in said step (ai) and a member that is selected of the group consisting of porous media having a pore size at least larger than approximately the maximum pore size of said zeolite from step (ai) and when more than about 10 Angstroms in said step (a-ii). In another preferred modality, step (a) comprises: (ai) adsorptive separation of the hydrocarbon-based feedstock in a flux enriched with non-cyclic aliphatic hydrocarbons comprising linear and branched non-cyclic aliphatic hydrocarbons (such as the desirable types described above) and a first flow of reject material comprising at least an increased proportion of hydrocarbons j ^^^ i ^^^^^^^^^^^^^^^^ »^«. ^ «« | j ^^ ^^^^^^ ^ | ^^ ^ J ^ | jy ^^ ^ cyclic and / or aromatic with region to said hydrocarbon feedstock, followed by (a-ii) adsorptive separation of said flux enriched with non-cyclic aliphatic hydrocarbons in said flux enriched with branched compounds and enriched with compounds linear; wherein said adsorptive separations are achieved using said adsorptive separation means with simulated movement bed. Unless otherwise indicated herein, "flux enriched with branched compounds" is the final flow of step (a); additional qualifiers such as "intermediate" will be somehow prefixed in the name to indicate that the flow, although rich in branched hydrocarbons, requires additional treatment before proceeding from the adsorptive separation steps of the present process to other steps. It should further be noted that step (a), the adsorptive separation step, can freely include other conventional, optional steps, such as distillation, provided that the adsorptive separation is carried out. Therefore, current commercial plants using the MOLEX® process will typically also include distillation at this stage and may be of use here. The invention further encompasses a process in which said first flow of reject material in step (ai) further comprises undesired branched hydrocarbons which are selected from branched hydrocarbons with geminal dimethyl, branched hydrocarbons with ethyl and hydrocarbons with branching greater than of ethyl; and in which said flow enriched with non-cyclic aliphatic hydrocarbons and the flow enriched with branched compounds each comprise a reduced proportion of said branched hydrocarbons with geminal dimethyl, hydrocarbons branched with ethyl and hydrocarbons cop, - branching higher than that of ethyl * > _ _. 5 in relation to said hydrocarbon-based feed material. In such embodiments, the flow compositions can be achieved by selecting as porous media: a member that is selected from the group consisting of zeolites with pore size of 4-5 Angstroms in said step (a-ii) and a member that is selected from the group consisting of porous media having a pore size at least greater than approximately the maximum pore size of said zeolite from step (a-i) and when more approximately 10 Angstroms in said step (ai). More generally, the invention relates to a method in which step (a) comprises the use of at least a porous medium that is selected from the group consisting of porous media having a minimum pore size larger than the pore size required for the selective adsorption of linear non-cyclic hydrocarbons, said pore size being no greater than about 20 Angstroms . As indicated, the preferred methods in the present include those in which the alkylation step, (c), has a selectivity to the internal isomer from about 0 to 20; in addition, a preferred alchemizing step, (c) uses a catalyst for alkylation consistent with said selectivity to the internal isomer, and in the which said alkylation catalyst is selected from the group consisting of at least partially acidic mordenites and at least partially acidic zeolite beta. Preferred alkylation catalysts include H-mordenites and H-beta, preferably H-mordenite, which is at least 5 partially dealuminized. With respect to the manufacture of modified alkylbenzenes and modified alkylbenzene sulphonates, the invention preferably also includes the process wherein said hydrocarbon-based feedstock comprises at least about 10% of branched methyl branched paraffins having molecular weight of at least about 128 and not more than about 282; said process having the step of dehydrogenation (b). More preferred in such embodiments, said hydrocarbon-based feedstock comprises at least about 20% branched paraffins with methyl having a molecular weight of at least 128 and no more than 226; said process having the dehydrogenation step (b) and having the alkylation step (c); and also preferably includes the process in which said hydrocarbon-based feedstock comprises at least 10% of branched olefins with methyl having a molecular weight of at least about 126 and not more than about 280. More preferably in such embodiments, the hydrocarbon-based feedstock comprises at least 50% of methyl branched olefins having a molecular weight of at least about 126. and of ^^ ** " no more than 224; said process does not have the step of dehydrogenation (b). For the corresponding process in which a modified primary OXO alcohol is manufactured, the above scales can be extended in some way, consistent with reaching a total carbon number of from 5 to C20 or higher. In a way rsá? Preferably, the paraffin molecular weight upper end of 226 supra extends to about 254, and the olefin molecular weight upper end of 224 supra, extends to about 252. Of significant utility to the detergent manufacturer, the material The hydrocarbon-based feedstock or supply material herein may be a refining or effluent of the adsorptive separation that is obtained from a linear alkylbenzene manufacturing process, or from a conventional linear detergent alcohol process. The methods of the present may have one or more steps after the alkylation step. Such steps may include the additional step of (d) sulfating the product of step (c). The sulfonation can be followed by the additional step of (e) neutralizing the product of step (d). Such steps may be followed by (f) mixing the product of step (d) or (e) with one or more adjunct materials for cleaning product; forming in this way a cleaning product. Therefore the method of the present invention includes highly preferred embodiments that have all the additional steps of j ^ j ^^ - ^ - ^ - fe- '' - - '^^ - ^^^^^. JgflL ^ h ^ l. (d) sulfonate the modified alkali metal product of step (c); (e) J? neutralizing the modified alkenylbenzenesulfonic acid product of step (d); and (f) mixing the modified alkylbenzene sulfonic acid product or modified alkyl benzene sulphonate surfactant of steps (d) or (e) with one or more adjunct materials for cleaning product; forming in this way a cleaning product. In one such embodiment, prior to said sulfonation step, the modified alkylbenzene which is the product of step (c) is combined with a linear alkylbenzene produced by a conventional process. In another such embodiment, at any step subsequent to the sulfonation step, the modified alkylbenzene sulfonate which is the product of step (d) is combined with a linear alkylbenzene sulfonate produced by a conventional process. In these combination modalities, a preferred process has a ratio of modified alkylbenzene to linear alkylbenzene from about 1: 100 to about 100: 1. When a relatively more linear product is desired, a preferred ratio is from about 10:90 to about 50:50. When a relatively more branched product is desired, a preferred ratio is from about 90:10 to about 51:49. The present invention also encompasses modified alkylbenzene produced by any of the methods herein; as well as modified alkylbenzenesulfonic acid or modified alkyl benzene sulphonate surfactant in any known salt form such as _ _ _ _ _ / B fo A »» Efeafefi? A? 5 the sodium salt form, the potassium salt form, the ammonium salt form, the substituted ammonium salt form or the like, produced by any of the procedures of this; as well as consumer cleaning products produced by any of the methods herein. The cleaning product embodiments herein include laundry detergents, dishwashing detergents, hard surface cleaners and the like. In such embodiments, the modified alkylbenzene sulfonate content, or the content of any surfactant derived from modified primary OXO alcohols, etc., herein and produced by the method herein is from about 0.0001% to about 99.9%, typically from about 1% to about 50%, and the composition further comprises from about 0.1% to about 99.9%, typically from about 1% to about 50%, of adjuncts for cleaning products such as co-surfactants, builders, enzymes, bleaches , promoters, activators or bleach catalysts and the like. Preferred consumer cleaning products produced by these methods suitably comprise from about 1% to about 50% of said modified surfactant and from about 0.0001% to about 99% of adjuncts for cleaning products^^ #gi | | j selected from enziá | ps, non-phosphate builders, polymers, activated bleach, catalyzed bleach, photobleach and mixtures thereof.

Alternate Methods of the Process The present invention has alternate embodiments in which two particularly shaped adsorptive separations are followed by additional steps which lead to useful cleaning surfactants. Therefore, a process comprising: (I) is encompassed herein Separating a hydrocarbon-based supply material into a flux enriched with branched hydrocarbons comprising, more preferred consisting essentially of, at least 85% of saturated non-cyclic aliphatic hydrocarbons having a carbon content from about C8 to about C20 , comprising said flow enriched with branched hydrocarbons at least 10% of paraffins having methyl branches, said methyl branches being distributed in said paraffins in such a way that any paraffin molecule has from 0 to no more than about 3 of said methyl branches and said branches being placed within said paraffins to a degree in which at least 90% of said branches occupy different positions than those which form portions of geminal dimethyl and / or quaternary portions; wherein said separation is conducted with means including at least two separation steps ? m -, p -,. ^^ u? ^ n i m ^ i t ^^^^^? adsorptive using said adsorptive separation means with simulated movement bed and at least two porous media having different pore sizes; and (II) converting said flux enriched with branched hydrocarbons to a surfactant by additional steps that include at least one step that is selected from: dehydrogenation, chlorination, sulfoxidation, oxidation to a C8-C20 alcohol and oxidation to a C8-C20 carboxylic acid or salt thereof; optionally followed by a step of: glucosamidation, conversion to an amide-based surfactant not derived from saccharide and sulfonation as the ester. Also by way of alternative embodiments, a process is comprised herein comprising: (I) separating a hydrocarbon-based feedstock into a flux enriched with branched olefinic hydrocarbons comprising, more preferred consisting essentially of mixtures of olefinic non-cyclic aliphatic hydrocarbons having a carbon content from about C8 to about C20 or mixtures thereof with their saturated analogs, said flow enriched with branched hydrocarbons comprising at least 10% of the sum of said olefins and their saturated analogues having methyl branches, said 20 methyl branches being distributed in said mixtures in such a way that any of the non-cyclic aliphatic hydrocarbon molecules have from 0 to no more than about 3 of said methyl branches and said branches being placed within the molecules of aliphatic hydrocarbon not XÜ *. . '^ and ~ ^ it'. . .. Y . ^ - - - *** - * fe ^ * »» l * ~~ .J-. The cyclic to a degree in which at least 90% of said branches occupy positions different from those that form portions of geminal dimethyl; wherein said separation is conducted by means including at least two adsorptive separation steps using adsorptive separation means with simulated movement bed and at least two porous media having different pore sizes; and (II) converting said enriched flow with olefinic branched hydrocarbons to a surface active agent by additional steps that include at least one step that is selected from: alkylation with benzene or toluene optionally followed by sulfonation; alkylation with phenol followed by at least one alkoxylation step, sulfation, sulphonation or combinations thereof; hydroformylation optionally followed by at least one alkoxylation step, alkoxylation combined with oxidation, glycosylation, sulfation, phosphating or combinations thereof; sulfonation; epoxidation; bromohydration followed by amination and oxidation to amine oxide; and phosphonation. In view of the alternate processes encompassed, the invention also encompasses the surfactants produced by such processes and the cleaning products produced by such processes. In the following, aspects of the invention will be described and illustrated in greater detail.

Modified alkylbenzene and alkylbenzene sulfonate products As indicated in the brief description of the invention, the present invention includes a process for preparing modified alkylbenzene sulfonate based surfactants suitable for use in cleaning products such as laundry detergents, hard surface cleaners, detergents for dishwashing and the like. The terms "modified alkylbenzene sulfonate-based surfactant" and "modified alkylbenzene" refer to the products of the processes herein. The term "modified" as applied to either novel alkylbenzene sulfonate based surfactants or novel alkylbenzene (MAB) surfactants is used to indicate that the product of the present process is of a composition different from that of all alkylbenzene sulfonate based surfactants used up to nowadays in the trade in cleaning compositions for the consumer. More particularly, the compositions herein differ in composition from the so-called "ABS" or poorly biodegradable alkylbenzene sulphonates, and from 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. Others Commercial LAS-based surfactants include LAS made by the DETAL® process. Preferred alkylbenzene sulphonate based surfactants herein which are made using the alkylation step with low selectivity to the preferred internal isomer herein are also different in composition from those made by alkylation of linear olefins using catalyst systems at Fluorinated zeolite base, which is believed to also include fluorinated mordenites. Without being limited by theory, it is believed that the modified alkylbenzene sulfonate 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, obtaining a content of 2-phenyl isomer of at least 25% and commonly 50% or even 70% or plus. In addition, the modified alkylbenzene sulfonate-based products herein differ in physical properties of the known alkylbenzene sulfonate based surfactants, for example by having an improved surfactant efficacy and a low tendency to phase-separate the internal isomers from the solution, especially in the presence of water hardness. gjk * Feeding materials and process flows The term "feedstock" is used herein to identify a material that has not yet been processed by the present method. However, the term "feed material" can also be used when a step, which is optional in the present method, has been applied to such a material, (for example, adsorptive separation on 5 Angstroms Ca zeolite) with the proviso that such treatment is presented before the first essential step of the present process. The term "flow" is used herein to identify materials that have gone through at least one step of the present process. The term "branched-chain enriched stream" herein, unless indicated more particularly, refers to any processed hydrocarbon fraction that contains at least the smallest amount of the following: (i) in relative terms , an increase of at least 10%, preferably at least 100% (i.e., twice), more preferred triple, quadruple or more, of non-cyclic branched hydrocarbons from C8 to about C20, compared to a fraction or original feeding material which has not been processed in the present procedure; or (ii) in absolute terms, at least approximately 5%, preferably 10% or more, of branched non-cyclic hydrocarbons from C8 to about C20, more preferred from about C10 to about C14 when the process produces modified alkylbenzenes or modified alkylbenzene sulphonates. The hydrocarbons to which reference is made may be olefinic, paraffinic or olefin / paraffin mixed in any ratio unless otherwise indicated more particularly (Certain preferred procedures involving the manufacture of modified primary OXO alcohols as illustrated in FIG. Figure 9 and above are based on paraffinic feed materials, although, more generally, variations in those procedures can utilize olefinic feedstocks.The branches are preferably monomethyl branches or isolated dimethylic branches (not gemimals). flow enriched with linear compounds "in the present unless indicated more particularly, refers to any fraction of processed hydrocarbon containing a percentage by weight of normal non-cyclic hydrocarbons (n-) greater than that of a fraction or original feedstock which has not been processed in the present procedure. More particularly, "rich in linear compounds" refers to any hydrocarbon fraction that contains at least the smallest amount of the following: (iii) in relative terms, an increase of at least 10%, preferably at least 100% (i.e., twice), more preferably triple, quadruple or more, of linear non-cyclic hydrocarbons from C8 to about C20, compared to a fraction or original feedstock which has not been processed in the present method; or (iv) in absolute terms, at least about 5%, preferably 10% or more, of linear non-cyclic hydrocarbons from C8 to about C20. The linear hydrocarbons may be olefinic, paraffinic or olefin / paraffin mixed in any ratio, unless otherwise indicated more particularly. Qualifiers such as "intermediate" when used in conjunction with a flux enriched with branched compounds are used to identify that the flux enriched with branched compounds referenced 15 has not completed the passage through the adsorptive separation step (a ) of the present procedure. Other qualifiers such as "olefinic" or "paraffinic" can be used to identify whether the stream contains a greater amount of olefinic hydrocarbons or paraffinic hydrocarbons. Feeding materials and flows in the present The process with respect to modalities comprising alkylation and with respect to embodiments comprising OXO reaction (or the concurrent use of both) are further illustrated in the following table. The numbers in the leftmost column refer to the feeding materials ^, ^^^ .-,? ^^ nrfm * - ^^ - * - • - ** ** - "* - -» ** - * - • and the flows identified in figure 1 to figure 18 . ^ ju ^^^^ n ^^ jjjÉi j a ^ ¡gj ^^ j * 3aj 10 fifteen twenty fifteen 200 0 The hydrocarbon-based feedstocks exemplified in the above chart herein should of course be considered as illustrative and not as limiting of the present invention. Any other suitable feeding material can be used. For example, fractionated petroleum wax materials that include fractionated Fischer-Tropsch wax materials. These waxes come from the distilled fractions of lubricating oil and melt on the scale relatively low of up to 72 ° C, for example, on the scale from about 50 ° C to about 70 ° C and contain from about 18 to about 36 carbon atoms. Such waxes preferably contain from 50% to 90% of normal alkanes and from 10% to 50% of monomethyl-branched alkanes and low levels of various alkanes cyclic. Such feedstocks based on fractionated materials are especially useful in the alternative embodiments of the invention as is further described in detail herein below, and as described in "Chemical Economics Handbook", published by SRI, Menlo , ... ^ fe ^. ^,. ^,: «- *« ** * • "" "- • - ~ ....'-? - and * * a ~ * ~ u * £ See, for example, "Waxes", S595.5003 L, published in 1995. The medical waxes are also described in Kirk Othrner's Encyclopedia of Chemical Technology, 3rd edition, (1984), volume 24. See "Waxes" on page 473. Any of the equivalent hydrocarbon-based feedstocks or more preferred shorter chain equivalents on the C10-C20 scale and having appreciable monomethyl branching at any position in the range are also suitable. The chain, for example those from the Fischer-Tropsch synthesis, The hydrocarbon-based feedstocks herein may contain varying amounts of N, O, S impurities. Certain preferred hydrocarbon-based feedstocks, especially if they are obtained from fractions containing sulfur and / or nitrogen, they are desulfurized and / or released from the nitrogenous matter using conventional desulphurisation technology or "de-NOS". The hydrocarbon-based feedstocks herein can be separated before being used in the present process so that the maximum amount of hydrocarbons having specific chain lengths and / or branching grades are most effectively used to make alkylbenzenes modified and / or modified primary OXO alcohols. For example, although not specifically illustrated in the figures, it may be desirable to use two portions of paraffin from kerosene for two essentially parallel procedures, each as described herein, including one an alkylation step to form modified alkylbenzene, and one including an OXO step to form modified primary OXO alcohols. In such a double process, it would typically be preferred to use a portion having a lower total carbon number for the manufacture of modified alkylbenzene (for example, a portion rich in C11-C13 hydrocarbons), while a heavier portion, for example one richer in hydrocarbons of C14-C17 could be used to elaborate modified primary OXO alcohols. Other changes in the process include the use of multiple streams or portions of hydrocarbons to concurrently manufacture modified and unmodified (conventional) alkylbenzenes and / or OXO alcohols.

Adsorptive separation step (s) In general, the separation techniques in step (a) or step (A) of the present process are based on adsorption on porous media and / or the use of clathrates. A prominent patent on adsorptive separation is US Patent 2,985,589, which illustrates devices, adsorbent beds, and temperature and pressure conditions generally suitable for use herein. The '589 patent does not disclose critical modifications, especially the pore sizes for specific separations and the connection of the passages, which are part of the present invention. The adsorptive separation steps of the present may, in general, be carried out in the vapor phase or in the liquid phase, and may or may not ^^^ ^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Use any of the processed processing equipment as identified in the section of the invention. The porous media used as adsorbents can in general be dry or non-dry. Preferred embodiments include those in which the adsorbents are dry and contain less than about 2% free moisture. Any of the adsorptive separation steps in accordance with the present invention may, or may not, use a desorbent or displacement agent. In general, any means of desorption may be used, such as a pressure stroke or other means. However, such a desorbent agent is preferably used, in other words, the displacement of the solvent is a preferred method to desorb the flows of the porous medium used herein. Suitable deadsorbents or displacement agents include a low molecular weight n-paraffin such as heptane, octane or the like, or a polar desorbent such as ammonia. It should be understood that, without regard to their presence, such well-known desorbentifiers, being completely conventional, are not explicitly included in identifying any of the fluxes or their compositions in the methods herein, and can be recirculated at will using recirculation steps of desorbent. which are not explicitly shown in Figures 1-18. hydrocarbons with geminal dimethyl, while at the same time they are small enough to exclude at least partially branched hydrocarbons with geminal dimethyl, ethyl and branches higher than ethyl as well as cyclic hydrocarbons (with rings of five, six or more members) and aromatic hydrocarbons . Such pore sizes large enough to retain appreciable amounts of methyl branched hydrocarbons are not invariably used in the conventional manufacture of linear alkylbenzene and in general are rarely used in any of the commercial processes unlike zeolites with pore size of 4. -5 Angstroms which are more familiar. The largest pore porous media are those used in Figures 1-7 in the adsorptive separation units marked "SOR 5/7". The essential porous media in step (a) or step (A) of the present therefore have a minimum pore size larger than the pore size required for the selective adsorption of linear non-cyclic hydrocarbons, i.e., higher that of those used in the conventional manufacture of linear alkylbenzene, said pore size being no greater than about 20 Angstroms, preferably no greater than about 10 Angstroms and more preferred, from about 5 Angstroms to about 7 Angstroms on average. When specifying the minimum pore size for the so-called "larger pore" porous materials herein, it should be recognized that such materials often have elliptical pores, for example SAPO-11 has a pore size of 4.4 by 6.7 Angstroms (5.55 Angstroms on average). See S. Miller, Microporus Materials, volume 2, pages 439-449 (1994). When comparing such material with a "smaller pore" zeolite such as a 4-5 Angstrom uniform pore zeolite, the convention here is to observe the average of the elliptical dimensions or the largest elliptical dimension-in any event not to the smallest elliptical dimension - when the size comparison is made. Therefore the material SAPO-11 hereby by definition has a larger pore size than that of a uniform pore zeolite of 5 Angstroms. The porous media having the largest essential pores in stage (a) or stage (A) herein can be either zeolites (aluminosilicates) or non-zeolites. Suitable non-zeolites include the silicoaluminophosphates, especially SAPO-11 although other silicoaluminophosphates may be used, for example SAPO 31 or 41, if the average pore size is greater than about 5 Angstroms or if elliptical pores are present with at least one elliptical dimension above 5 Angstroms. Another suitable technique for adsorptive separation in the present is sorption using pyrolyzed polyvinylidene chloride, ie pyrolized SARAN, for example manufactured in accordance with the application of the Netherlands NL 7111508 published on October 25, 1971. Preferred materials have sieve diameter from 4-7 Angstroms. When such material is used as the essential adsorbent, a size of tf l? r? ai8S-tt-ti r? ? f - "" i - '' * Aa- ^ * • * - • - • * • - * ^^ pore above about 5 Angstroms.

Use of grafted mordenites with organometallic compound and other grafted zeolites as porous media in step r. t (a) or step (A) The present invention also includes useful embodiments in which the adsorptive separations of step (a) or step (A) comprise at least one separation step using a mordenite grafted with organometallic compound . Especially suitable as the porous means of "larger pore" herein are grafted mordenites such as tin-grafted mordenite. Similarly, and more generally, the invention encompasses a method comprising the use of a grafted mordenite to make detergent surfactants and any of the corresponding surfactants and consumer products produced by using these specific porous media in any of the the procedures defined above. See document EP 559, 510 to 9/8/93 incorporated by reference in its entirety. The practitioner will choose those grafted mordenites of EP 559,510 which are easily identifiable from the examples thereof which will be the most appropriate for separating linear and monomethyl-branched hydrocarbons from hydrocarbons with geminal dimethyl and polymethylated.

Other grafted zeolites useful as the porous media herein include those of US 5,326,928, also incorporated by reference in their entirety. In such embodiments of the present invention, it is especially preferred to integrate in a single procedure the use of both of the grafted mordenite identified above in step (a) and the use of at least partially dealuminated H-mordenite in step (c) ), the alkylation step defined elsewhere in the present. On this basis, using the terminology of US 5,326,928 to describe the process module containing the grafted component and combining therewith the preferred alkylation step as defined in the present invention, the present invention also encompasses a process for making alkylbenzenes Modified and / or modified alkylbenzene sulphonates, said process comprising: (a) at least one step of removing the aliphatic paraffins having varying degrees of branching in a hydrocarbon filler containing molecules of 9 to 14 carbon atoms in at least one first effluent comprising less branched paraffins (linear and monomethyl, optionally some dimethyl-branched) and in at least one second effluent comprising more branched paraffins (trimethyl-branched paraffins and paraffins with higher branches and optionally cyclic and / or aromatic impurities), comprising said separation po The hydrocarbon charge is contacted with at least one adsorbent bed comprising at least one microporous solid (as defined in US Pat. No. 5,326,928) which has an organometallic compound of a sufficient amount and form in the pores thereof. produce selective pores for entry of less branched paraffins but not for more branched paraffins; (b) at least one step of renting a less branched effluent from step (a), preferably into an alkylation having an internal isomer selectivity of from 0 to 40, and even more preferred, using an H-mordenite by at least partially dealuminated, at least partially acidic as the catalyst; and (c) at least one step to sulfonate the product of step (b) using any conventional sulfonation agent. The resulting modified alkylbenzene sulfonic acid can be neutralized and incorporated into cleaning products as taught elsewhere herein. In step (a) or step (A) of the present process, there is a preference to use zeolites or other porous media in a form such that they do not actively promote the chemical reactions of the supply material, for example fractionation, polymerization. Therefore, acid mordenite is preferably avoided in step (a) or step (A). See, on the other hand, the catalysts for later alkylation in the present, in which the at least partially acidic forms are preferred.

Porous media (of smaller pore types) The smallest pore zeolites optionally useful in step (a) or step (A) herein, for example those used in processes such as those of the adsorptive separation unit identified as "SOR 4/5" in figures 1, 2, 5, 6, 9, etc., are those that selectively adsorb linear hydrocarbons and which do not appreciably adsorb the branched hydrocarbons with methyl. Such porous materials are well known and include, for example, calcium zeolites with pores of 4-5 Angstroms. Such materials are further illustrated in US 2,985,589 and are those that are in commercial use today for the manufacture of linear alkylbenzenes.

Porous Medium (for example OLEX® process or the like) When making primary OXO alcohols modified herein, it may be desirable to conduct an olefin / paraffin separation step in step (C) to concentrate mono-olefins. See "SOR O / P" in the figures and step (C) in the claims. Porous media suitable for this step include zeolite X or zeolite Y treated with copper or silver. Consult, for example, US 5,300,715 or US 4,133,842, and references cited therein. See also US 4,036,744 and US 4,048,111. Alternatively, UOP Corp., a technology licensee, has a complete procedure known as OLEX® available for licensing.

• "^ ^ H ^. Syy.¿- * f" -fe »Jl '} The formation of clathrates The formation of clathrates with urea can also be used here in step (a) to separate n-paraffins from branched paraffins, as is well known in the art. See, for example, Surfactant Science Series, Marcel Dekker, N.Y. 1996, volume 56, pages 9-10 and references therein. See also "Detergent Manufacture Including Zeolite Builders and Other New Materials", Ed. Sittig, Noyes Data Corp., New Jersey, 1979, pages 25-30 and especially US 3,506,569 incorporated in its entirety which uses solid urea and solvents not chlorocarbons. More generally but less preferred, the methods according to US 3,162,627 can be used.

Dehydrogenation In general, dehydrogenation of the olefin or olefin / paraffin mixtures in the present invention can be achieved using any of the known dehydrogenation catalyst systems, including those described in the Surfactant Science Series references cited in the Background Art section 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 gas and a precious metal-based catalyst is commonly present (eg DeH-5®, DeH-7®, DeH-9® available from UOP) although metal-free dehydrogenation systems can alternatively be used precious and without hydrogen such as a zeolite / air system without precious metals being present . More specifically, the dehydrogenation catalysts useful in the present invention include an alum-supported catalyst containing Sn and having Pt: 0.16%, Ir: 0.24%, Sn: 0.50% and Li: 0.54% as described in US Pat. 5,012,027 incorporated by reference. This catalyst, when placed in contact with a mixture of C9-C14 paraffins (thought to be linear) at 500 ° C and 0.68 atm. it produces olefinic products (38 h in the flow) with 90.88% selectivity and 11.02% conversion and it is believed that it is very appropriate to dehydrogenate at least partially flows rich in branched paraffin compounds herein. See also documents US 4,786,625; EP 320,549 A1 6/21/89; Vora et al., Chem Age India (1986), 37 (6) 415-18. As indicated above, the dehydrogenation can be total or partial, more typically partial. When it is partial, this step forms a mixture of olefins (for example, about 10% although this amount is illustrative and should not be considered as limitation) and the rest are unreacted paraffins. Such a mixture is a suitable feedstock for the alkylation step of the present process. Other useful dehydrogenation systems readily adapted in the present invention include those of US 4,762,960 incorporated by reference which discloses a catalyst for dehydrogenation containing metal of the Pt group having a metal modifier which is selected from the group consisting of Sn, Ge, Re and their mixtures, an alkali metal, an alkaline earth metal or mixtures thereof, and a particularly defined refractory oxide support. Catalysts for dehydrogenation and alternative conditions useful in the present invention include those of US 4,886,926 and US 5,536,695.

Alkylation Important embodiments of the present invention further include alkylation, which is carried out after deslinealization by separative enrichment of slightly branched paraffins and at least partial dehydrogenation of the de-linearized olefin or paraffin / olefin mixtures. The alkylation is carried out with an aromatic hydrocarbon which is selected from benzene, toluene and mixtures thereof.

Selectivity towards the internal isomer and selection of an alkylation step Preferred embodiments of the methods of the present invention require an alkylation step having a selectivity to the internal isomer on the scale from 0 to 40, preferably from 0 to 20. , even more preferred from 0 to 10. The selectivity towards the internal isomer or "US" as defined in the present invention is measured for any given alkylation process step by conducting a benzene alkylation test for 1 -dodecene at a molar ratio of 10: 1. The alkylation is carried out 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 selectivity towards the internal isomer is determined as: IIS = 100 * (1-quantity of terminal phenyldodecanes) the 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 The sum of 2-phenyldodecane and 3-phenyldodecane and 4-phenyldodecane and 5-phenyldodecane and 6-phenyldodecane and wherein said amounts are determined by any known analytical technique for alkylbenzene sulfonates such as gas chromatography. See Analytical Chemistry, Nov. 1983, 55 (13), 2120-2126, Eganhouse et al, "Determination of long-chain 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 1 from the result and ^^^ multiplying by 100. Of course it should be understood that the specific alkenes used to characterize or prove any given step of alkylation in terms of their appropriateness are reference materials that allow a comparison of the alkylation step of the present with 5 steps of known alkylation as used in the preparation of linear alkylbenzenes and which enable the practitioner of the invention to decide whether a known known alkylation step is, or is not, useful in the context of the series of process steps constituting the present invention. In the process of the invention as practiced, the hydrocarbon-based sourcing material for alkylation normally used is of course that which is specified on the basis of the preceding process steps. It should also be noted, that all current commercial processes for manufacturing LAS are excluded from the preferred embodiments of the present invention solely on the basis of US for the alkylation step. For example, LAS methods which are based on aluminum chloride, HF and the like all have a US outside the scale specified for the process herein. On the contrary, a few steps of alkylation described in the literature but not currently applied in the commercial production of alkylbenzene sulfonate have appropriate 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 further examples.

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 data on well-documented alkylations. For example, the appropriate conditions of procedure for determining whether an alkylation with AICI3 can be used herein are exemplified by a reaction of 5% molar AICI3 relative to 1 -dodecene at 20-40 ° C for 0.5-1.0 hours in a batch reactor. Said test demonstrates that an alkylation step with AICI3 is inappropriate for use in the present process. A US of about 48 should be obtained. In another example, an appropriate alkylation test using HF as a catalyst should give a US of about 60. Thus, neither the alkylation with AICI3 nor the alkylation with HF are 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 US 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 "1 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. Temperatures and pressures are expected for the mordenite alkylation test example (see also detailed examples of the methods present later herein), they are generally more useful for testing zeolites and other form-selective alkylation catalysts using a catalyst such as H-ZSM- 4 you should get a US of approximately 18. Clearly both alkylations catalyzed with dealuminated molarite and H-ZSM-4 give US acceptable for the invention, with mordenite being superior. Without intending to be limited by theory, it is believed that the low US alkylation step practiced using H-mordenites in the present is able not only to rent benzene with the hydrocarbon rich in branched compounds, but also, very useful, can change the position of a branch with methyl attached to the hydrocarbon chain. ma? ? iíillb ^? 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 zeolites, non-acidic calcium mordenite, and many others. In fact, no alkylation catalyst currently used for alkylation in the commercial production of linear alkylbenzenesulfonates for detergents has yet been found suitable. 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 the form of less partially acidic. 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. t ^^. , ^, ^ -.- ^^ ^. ^ .. ^ ^. . ^ ¿É M ^^^^ 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. The calcite form of completely exchanged mordenite, for example, is inappropriate while 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 step 7 in Figure 1. The pores that characterize the zeolites useful in the present alkylation process can be substantially circular , such as in the cancrinite which has uniform pores of approximately 6.2 Angstroms, or preferably may be somewhat elliptical, such as in the 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 in size. of relatively small pore 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 earths, 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 upon calcining give the hydrogenated form. This exchange is conveniently carried out by contacting the zeolite with an ammonium salt solution, for example, of ammonium chloride, using well-known ion exchange techniques. In certain preferred embodiments, the degree of replacement is such as to produce a zeolite material 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 zeolites they can, 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 matrix resistant to temperature 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 montmorillonite and kaolin families, whose families include the sub-bentonites and the kaolins commonly known as clays Dixie, McNamee-Georgia and Florida or others in which the main mineral constituent is haloisite, kaolinite, diquita, nacrita 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, silica-zirconium, silica-thorium, silica-beryllium and silica-titanium, as well as combinations ternary, such as silica-aluminum-thorium, silica-aluminum-zirconium, silica-aluminum-magnesium, and silica-magnesium-zirconium. 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% in 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 relationships silica: alumina referred to in this specification are structural or framework relationships, ie, the ratio for the tetrahedron SiO4 to the AIO4. 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 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 (TGA) 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 from the structure of zeolite. Therefore, care must be taken to ensure that the relationship of the silica: alumina structure is determined correctly. The appropriate beta zeolite for use in the present (but less preferred than H-mordenite) is described in the patent E.U.A. No. 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 from of the training solution. These can be activated by heating them in an inert atmosphere at 540 ° C for 1 hour, for example, followed by base exchange with ammonium salts and then calcination at 540 ° C in air. The presence of organic cations in the formation solution may not be ^, ^, ^^^. ^ ^^^ * ~ * ^ .. ---. - - -. I? Gi fet ^ ^ absolutely essential for the formation of 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 base exchange, 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 aluminum atoms per 1000 cubic Angstroms, as given, for example, on page 19 of the article Zeolite Structure 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 that contains enough NH4NO3 to completely exchange the Na atoms with NH4 ions and H atoms. The resulting zeolites can have a SiO2: AI2O3 ratio of 15-26 (preferably 17-23): 1 and Preferably they are calcined to at least partially convert the NH4 / H form to an H form. Optionally, although not necessarily desired in particular 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 acid mordenite-based catalyst useful for the alkylation step herein is described in the U.S.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 catalysts based on acid mordenite useful for the passage of Alkylation in the present include those described in the patents of E.U.A. 5,243,116 and E.U.A. 5,198,595. Even another alkylation catalyst useful herein is described in the U.S.A. 5,175,135 which is an acid mordenite-based zeolite 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 on the scale 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 selectivity requirements towards the internal isomer identified above.

Distillation of modified alkylbenzenes or modified primary OXO alcohols Optionally, depending on the supply material and the precise sequence of steps used, the present process may include the distillation of modified alkylbenzenes or modified primary OXO alcohols, for example to remove unreacted starting materials, paraffins, excess 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) or OXO alcohols. Suitable distillation steps are described in the Surfactant Science Series review for manufacture of alkylbenzene sulfonate mentioned hereinbefore.

Sulfonation / Sulfonation and Treatment In general, the sulfonation of the modified alkylbenzenes or sulfonation of modified primary OXO alcohols (or their alkoxylates) in the present process can be achieved using any of the well known sulfonation systems, including those described in the volume "Detergent Manufacture Including Zeolite Builders and Other New Materials "referred to hereinbefore, as well as in the Surfactant Science Series review for manufacture of alkylbenzene sulfonate mentioned hereinbefore. Common sulfonation systems include sulfuric acid, chlorosulfonic acid, oil, sulfur trioxide and the like. Sulfur trioxide / air is especially preferred. Details of the sulfonation using a suitable air / sulfur trioxide mixture are provided in US 3,427,342, Chemithon. The sulfonation processes are also described extensively in "Sulfonation Technology in the .¿.afc ^^^^^^^^^ ^^^^^^^^^^^^^^^^ Detergent Industry ", WH of Groot, Küuwer Academic Publishers, Boston, 1991. Any convenient treatment step can be used in the present process.The common practice is to neutralize after the sulfonation with any suitable alkali. The neutralization can be carried out using a selected alkali of sodium, potassium, ammonium, magnesium and substituted ammonium and mixtures thereof Potassium can aid solubility, magnesium can promote the yield in soft water and substituted ammonium can be useful for formulating 10 specialty variations of the present surfactants The invention encompasses any of the forms derived from the modified alkylbenzene sulfonate surfactants, or the sulfated modified primary OXO alcohols, or the sulfated, alkoxylated modified primary OXO alcohols, such as produced by the present method, and its use in composi products for the consumer. Alternatively, the acid form of the present surfactants can be added directly to the acidic cleaning products, or can be mixed with cleaning ingredients and then neutralized. after the alkylation steps As noted, the method of manufacturing modified alkylbenzene herein includes embodiments having steps that take place after the alkylation step (c). This steps * - * X .... ^^. ^, Z. "Z ^ ^. «^ .. .. z, ft ^^^^ J ^ J ^^^ ^^ J to ^^^^^^ - ^^^ a ^ preferably nclude (d) sulfonating the product of step (c); and one or more steps that are selected from (e) neutralizing the product of step (d); and (f) mixing the product of step (d) or (e) with one or more adjunct materials for cleaning products, whereby a cleaning product is formed.

Mixed In a preferred embodiment, prior to said step of sulfonating the modified alkylbenzene modalities is the product of said step (c) is blended with a linear alkylbenzene produced by a conventional method. In another embodiment, at any step subsequent to said sulfonation step, the modified alkylbenzene sulfonate, which is the product of said step (d), is mixed with a linear alkylbenzene produced by a conventional process. In these mixed modalities, a preferred process has a modified alkylbenzene to linear alkylbenzene ratio from about 10:90 to about 50:50. The corresponding mixing schemes are of course also applicable in a similar manner to the modified primary OXO alcohol processes. In addition, any mixtures of the different types of surfactant, or their precursors, may be made herein. For example, the practitioner can freely blend modified alkylbenzene with modified primary alcohol OXO as elaborated herein, alkoxylate the mixture using ethylene oxide, propylene oxide, etc., and then sulfating / sulfonating the resulting mixture. In addition, because, in general, the modified OXO alcohols can be separated by distillation and various other OXO alcohols including linear OXO alcohol types are known in the art, the present invention also includes methods of mixing any of the modified OXO alcohols. or branched which are hereby obtained with any linear OXO alcohol in any proportion, such as from 1: 100 to about 100: 1 by weight of branched: linear OXO alcohol, and to convert any of said mixtures of OXO alcohols to surfactants useful for detergents.

OTHER MODES OF PROCEDURE The present invention also encompasses a process for benefiting an effluent stream from the manufacture of linear alkylbenzene sulfonate based surfactants useful in cleaning products, said process comprising (i) at least partially isolating an isoparaffin in a flow enriched with normal paraffins and an effluent flow having the form of a flow enriched with isoparaffin (especially branched paraffin with methyl) comprising at least about 10% isoparaffin and having a molecular weight of at least about 128 and not more than about 282 wherein said separation comprises at least one step which is selected from clathrate formation by urea and separation by means of sorption and wherein said steps are integral in a process for making linear alkylbenzene; (Ii) at least partially further enriching the isoparaffin content of said effluent stream by at least one step selected from urea clathration and adsorptive separation; wherein said step is additional to comes after step (i); and (iii) an at least partial dehydrogenation step of the isoparaffin enriched stream of said step (ii). More generally, it is contemplated that the hydrocarbons produced herein may be useful not only in modified alkylbenzene sulfonate-based surfactants such as those illustrated in a non-limiting manner herein but also in modified surfactants other than alkylbenzene sulphonates (such as alkyl sulphates). Thus, the present invention also encompasses a method for benefiting a branched paraffinic effluent flow which comprises (i) separating at least partially an isoparaffin in a flow enriched with normal paraffin and an effluent flow having the form of a flow enriched with isoparaffin containing at least about 10% isoparaffin, wherein said separation comprises at least one step which is selected from formation of clathrates by means of urea and separation by sorption; (I) at least partially further enriching the isoparaffin content of said effluent stream by at least one step which is selected from formation of clathrates with urea and adsorptive separation; wherein said step is additional to and comes after step (i); and (ii) one step of dehydrogenation at least of the flow enriched with isoparaffin from said step (i). In such embodiments, the flow enriched with isoparaffin can vary from about C10 to about C20 in the total carbon content and the non-linear fraction of said enriched flow comprises an average from about one to about two different methyl side chains of the side chains of methyl terminals per molecule and in addition, the non-linear fraction of said enriched flux preferably comprises less than about 30%, more preferred less than about 10%, more preferred even less than about 1% of molecules having quaternary ammonium atoms and less than 50%, preferably less than about 10%, more preferred less than about 1% of molecules having geminal dimethyl substitution.

Process modalities that incorporate hydroformylation (OXQ reaction) As noted in the Brief Description, the present invention also has process embodiments that involve converting hydrocarbons, through certain adsorptive separation selections, into novel and useful modified primary OXO alcohols that can be used to manufacture sulfates exceptionally soluble, poly (alkoxy) sulfates and poly (alkoxylates). Those are only illustrative. Modified versions of any other types of surfactants known in the art that can be obtained from OXO alcohols are, of course, included in the present invention. With respect to said method of procedure, broadly defined in the Brief Description, a preferred method herein has in step (A) means comprising one, two or more of said devices and at least two of said beds, at least one of said beds comprises a porous medium which is different in relation to the content of porous medium from another of the beds by an increased capacity to retain non-cyclic aliphatic hydrocarbons branched with methyl. In addition, preferably, said step (D) comprises an OXO stage of a step in which the OXO catalyst is a transition metal coordinated with phosphine other than iron. In greater detail, in said process, at least one of the beds comprises conventional porous medium for the manufacture of linear alkylbenzenes, the at least one bed has a connection in the The process is suitable to at least partially increase the proportion of non-cyclic aliphatic hydrocarbons branched with methyl in streams passing to stage (B) of said process, and suitable to at least partially decrease the proportion of linear non-cyclic aliphatic hydrocarbons passing through to step (B) of said method, said Linear non-cyclic aliphatic hydrocarbons being at least partially removed as the flux enriched with linear compounds in said step (A). **. *:. - * - »*., * 7. jk ***, .. * - £ - • > - ' - 7 ', ^ z_h¡ ^^ i ^^^^^ Ü & gis! ¿^^^ t¡¡, 1Ó8 Conveniently, in one of said process modes, the adsorptive motion bed separation means simulated in step (A) comprises one of said devices, with the proviso that said device is capable of simulated movement of the porous medium in at least two of said at least one bed; or at least two of said devices. Also encompassed herein is the method in which there are two said at least one bed, each comprising a different number of porous medium, each of at least one bed being controlled by one of said devices, and each of said devices have a minimum of eight ports to achieve the simulated movement of the porous medium in said at least one bed. See, for example, Figure 9 in which the SOR unit 4/5 comprises a type of porous medium as defined in more detail elsewhere herein, and the SOR unit 5/7 comprises another type. The "devices" referred to can be selected especially from special rotary valve devices, as described in detail in several patents identified in the "Background Art" section. See also figure 8 in which, although more particularly illustrates a process having an alkylation step, more detail of a suitable arrangement of adsorptive separation units, rotary valves and complementary equipment is shown. It should be understood therefore that the devices, means and equipment of sorption, are all known individually; it's rather the selection of devices and - ^ -T "^ - - ------ and * - - - - ^ | ÜFaiÍ ^ A ^ - - Aa ^ '* < Í"' how to connect what is essential so that the purposes of the present invention reach higher OXO alcohols and the surfactants that can be derived. Accordingly the present invention also encompasses a method of the type of alcohol production OXO in which is present the flow enriched with linear compounds in said step (A) and said step (A) comprises: (Ai) adsorptive separation material hydrocarbon-based feed in flux enriched with linear compounds and a flux enriched with intermediate branched compounds and rejection of said flux enriched with linear compounds by means of an adsorptive separation medium of simulated movement bed; followed by (A-i) adsorptive separation of the branched intermediate enriched flow in branched-chain enriched compounds comprising an increased proportion of branched non-cyclic aliphatic hydrocarbons in relation to said intermediate enriched branched-chain flow, and said material flow rejection comprising at least an increased cyclic hydrocarbons and / or aromatic in relation to said flow enriched with branched compounds by other means adsorptive separation simulated moving bed proportion. Preferably in such embodiment, all beds comprise non-conventional porous medium for the preparation of linear alkylbenzenes (for example a SOR 5/7 unit containing SAPO-1 1 or another equivalent molecular sieve of a larger pore size of the ^ ^ .- ^ • - ^ ---- • - - •• - ^^ ^^ &. ^^^ ^ K, ^^^^^^^^ used in making linear alkylbenzenes) , said porous medium has suitable pore sizes for, and being connected in said process, in a manner consistent with at least partially increasing the proportion of branched hydrocarbons with methyl plus linear non-cyclic aliphatics in streams passing to step (B) of said process, and at least partially reduce the proportion of aliphatic, cyclic, aromatic and / or branched hydrocarbons with ethyl or with higher branching passing said process step (B), said hydrocarbons different from the linear and branched hydrocarbons with methyl being at least partially eliminated as a flow of reject material in step (A). Suitably in the OXO alcohol manufacturing embodiments of the present process, said hydrocarbon-based feedstock comprises at least 10% branched paraffins with methyl having a molecular weight of at least 128 and not more than about 282. Refer to the tables elsewhere herein for further description of suitable feedstocks. The raw feedstocks in the OXO alcohol process hereof are desirably distilled before used. For example, as illustrated in a non-limiting manner by the distillation unit at the beginning of the procedures shown in Figures 9-18. In this example the hydrocarbon-based feedstock (as it comes from said distillation unit towards the remaining of the process) comprises a narrow portion of no more than three carbon atoms (preferably not more than two carbon atoms) on the scale of C10 to C17. These portions may be portions of a single carbon, two carbon portions, portions of three carbons or portions comprising a non exact scale of carbon numbers, such as a portion of one half carbons. Suitable portions are further illustrated by a portion of C11-C13, a portion of C14-C15, and a portion of C15-C17, although this does not mean that it excludes other portions such as a portion of C16.5. Said portions designated by non-integer carbon numbers may be generated by any means, such as mixing fractions of a single shorter and longer carbon number. In this way, a portion of C16.5 can be made by mixing C16 and C17 or mixing C14 and C17, etc. Preferred portions have carbon numbers "stretched" narrower in a mixture. Alternatively, distillation could be performed directly on the flux enriched with olefinic branched compounds just prior to the OXO reaction on the flux enriched with olefinic branched compounds to produce the desired portion. It should be understood and appreciated, of course, for practical reasons that when hydrocarbons are distilled herein, the desirable methyl branched hydrocarbons will generally be lower boiling than linear hydrocarbons having a carbon number. Therefore, a preferred portion having a boiling point in a intermediate scale between a linear paraffin of C15 and a linear paraffin of C16 (and therefore apparently a portion having a non-whole carbon number) will be relatively rich in methyl branched isomers having a total of 16 carbon atoms which are desirable for the present method. In a very unusual, if not only, manner for an OXO alcohol manufacturing process, said hydrocarbon-based feedstock is a refined adsorptive separation material that is obtained from a linear alkylbenzene manufacturing process or a The conventional procedure of linear detergent alcohol. In other words, the present invention opens up all the ways of new possibilities to combine linear alkylbenzene manufacture and / or conventional linear detergent alcohol processes and manufacture of OXO alcohol in a manner that has not been achieved to date. This results in a better use of the feeding materials. Moreover, when the invention is used as taught herein, new alkyl benzenes and OXO alcohols are accessible. These can be manufactured by themselves, or they can be made in any swap with conventional linear alkylbenzenes and / or OXO alcohols by configuring the plant in a way using the steps that are taught in this. Once the modified primary OXO alcohol has been made, of course it can be in the same plant or in a remote installation in another useful derivative. For example, the present method may having the additional stage or steps in sequence selected from: (E) sulfatar and neutralizing the product of said step (D); (F) alkoxylating the product of step (D); and (G) alkoxylating, sulfating and neutralizing the product of step (D). In addition, once the surfactant derivatives of the above types have been manufactured, they can easily be incorporated into all types of cleaning compositions. For this purpose, whether placed in the same facility or located remotely, the present method may have the additional step of (H) mixing the product of the preceding 10 steps with one or more adjunct materials for cleaning products; thus forming a cleaning product. Although as will be seen from the Background Art section, several OXO alcohols are already well known, see for example the Shell and / or Sasol procedures, it has not been suggested previously to apply the specific types of adsorptive separation prior to the OXO stage. which are specifically identified in the present. Furthermore, it has not been suggested to use, at least with respect to detergents, parts of flows not useful to date available for the manufacture of linear alkylbenzene. Whether from the selection of unprocessed feedstock, or from the use of specific adsorptive separation stages, or both, the composition of the resulting OXO alcohols changes in relation to the Shell and Sasol procedures and makes them very useful for the manufacture of surfactants, especially for low wash temperatures, which demand solubility ^ fc ^^^^^^^^^^ ft ^^^^^^^^^^^^^^^^^^^^^^^^^^ * ^^^^^^^^^^ ^^^^^^; ^^^^ fe ^^ ¿^ ^ = a ^ B = ia ^^ | (compact granules, tablets) or applications of high water hardness. All this is achieved with great economy. In view of the changes in composition imparted to the OXO alcohols, the invention also encompasses modified primary OXO alcohol produced by any of the methods present. Also, the invention encompasses any consumer cleaning product produced by the process described above that includes the manufacture of specific OXO alcohol shown herein, followed by a step comprising mixing the minus one adjunct ingredient for cleaning product. In other variations, the methods of the present invention include those in which prior to said OXO step, (D), the product of step (B) or (C) is mixed with a conventional detergent olefin; or in which the product of any of the stages (E), (F) or (G) is mixed with an agent conventional detersive surfactant. Although there are many configurations in which the present process makes it possible to prepare alternately modified alkylbenzenes and modified primary OXO alcohols concurrently or in alternate process cycles, one such procedure according to The invention further comprises, in a non-limiting manner, at least one step of reacting the product of step (A) with an aromatic hydrocarbon selected from the group consisting of benzene, toluene and mixtures thereof in the presence of a catalyst for alkylation.; for making modified alkylbenzenes (of altered crystallinity), said catalyst for alkylation has a selectivity to the internal isomer from 0 to 40. Branches include checking that means are provided to direct the product from step (C) to step (D), at said alkylation step, or towards both stages in parallel. See figures for additional illustration. More generally, the invention also encompasses a detergent or cleaning composition comprising (a) an effective amount of a detersive surfactant is selected from the group consisting of alkyl sulfates, alkyl poly (alkoxy) sulfates, alkyl poly (alkoxylates) and mixtures thereof, said surfactant incorporates (preferably in an amount of up to one mole of, more preferably about one mole of) the radical RO of a detergent alcohol of R = C9-C20 of the formula ROH, in which R is mixtures of branched chains with methyl and some linear chains and said alcohol is further characterized in that it comprises the product of at least one Fischer-Tropsch process step or an oligomerization or dimerization or structure isomerization step or an olefin supply step and / or paraffin (for example through the previous adsorptive separations or alternate processes such as hydroisomerization / wax fractionation, Fle xicoking®, Fluidcoking®, etc.) and at least one stage of the OXO procedure; with the proviso that in at least one stage prior to the OXO process step an adsorptive separation step is present which has the effect of increasing the proportion of branched olefin with methyl which is used as feedstock in said process step OXO; and (b) one or more adjuncts that contribute at least partially to the useful properties of the composition. Also encompassed herein is a detergent or cleaning composition comprising (a) an effective amount of a detersive surfactant which is selected from alkyl sulfates, alkylpoly (alkoxy) sulfates, alkylpoly (alkoxylates) and mixtures thereof; said surfactant incorporates (preferably in an amount of up to one mole, more preferably d almost a mole of) the radical RO of a detergent alcohol of R = C9-C20 of formula ROH, in which R is mixtures of branched chains with methyl and some linear chains and said alcohol is further characterized in that it comprises the product of any of the modified primary OXO alcohol manufacturing processes described above; and (b) one or more adjuncts that contribute at least partially to the useful properties of the composition.

Modalities of cleaning products The cleaning product embodiments of the present invention include laundry detergents, dishwashing detergents, hard surface cleaners and the like. In such embodiments, the content of modified alkylbenzene sulfonate p surfactant derivative of modified primary OXO alcohol produced by the process herein is from about 0.1% to about 99.9%, typically from about 1% to about 50%, and the composition further comprises from about 0.1% to about 99.9%, typically from about 1% to about 50%, of adjunct materials for cleaning products such as co-surfactants, detergency builders, enzymes, bleaches, promoters, activators or bleach catalysts and the like. The present invention also encompasses a cleaning product formed by the present process, comprising: a) from about 0.1% to about 99.8%, more typically up to about 50%, of a modified alkylbenzene sulfonate surfactant or alcohol-derived surfactant Modified primary OXO such as modified alkyl sulfate, modified poly (alkoxy) sulfate, etc., as prepared herein and b) of about 0.00001%, more typically at least about 1% to about 99.9%, of one or more of said attached 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 levels, or, less common, higher. 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 C6-C16 oxybenzenesulfonates); preformed perishes related to, or based on any of the aforementioned bleach activators, detergency builders which include 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, soluble in water or insoluble in water, 2,2'-oxidisuccinates, 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 , agents antiredeposition, silicone / silica and other 'sj' foam pressors, hydrotropes, perfumes or pro-perfumes, dyes, photobleaches, thickeners, simple salts and alkalis such as those based on sodium or potassium which include hydroxides, carbonates, bicarbonates and sulfates, 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 in the present invention 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 that are supplied in compartment containers double, spray or foam detergents and other homogeneous or multiphase products J &. ', ~ £ ?: cleaning 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 higher, and may have a wide scale of alkalinity reserve which may include very high alkalinity reserves such as in uncovering uses of drains in which tens of grams of NaOH equivalent per 100 grams of formulation may be present, varying through the 1-10 grams of NaOH equivalent and the mild or low alkalinity scales of liquid hand cleaners, up to the acidic side as in the acid cleaners of hard surfaces. 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 including 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. 5 The consumer product cleaning compositions of the present invention include, but are not limited to: Lightweight Liquid Detergents (LDL) These compositions include compositions for LDL that have magnesium ions that improve surfactancy (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 surfactant skin sensing modifiers, emollient and / or enzymatic type, including proteases; and / or antimicrobial agents; the most complete 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; US 4,891, 147; US 5,006,273; US 5,021, 196; US 5,147,576; US 5,160,655) as "unstructured" or isotropic liquid types, and can in general be aqueous or non-aqueous (see, for example, EP 738,778 A, WO 97/00937 A, WO 97/00936 A; EP 752,466 A; 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 may 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, US Pat. , 848; US 5,445,756) 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, 4 31, 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 (HDG) These compositions include so-called "compact" or agglomerated or otherwise non-spray dried, as well as so-called "spongy" or spray-dried. Both types are included glass and mosaics, and cleaner s in apersal with bleach; bath cleaners including types for mold removal, those containing bleach, antimicrobials, acids, neutrals and basics. See, for example, EP 743,280 A; EP 743,279 A. Acid cleaners include those of WO 96/34938 A.

Laundry Bars and / or 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 9502668, 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" types as "with" .. ... ^^. Z .. - '. • ,. ^ .z &^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Such detergents may include the most common anionic surfactant-based types or may be so-called "highly nonionic surfactant" types in which commonly the non-ionic 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 5,573,697; WO 96/34082 A; US 5,569,645; 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 694,608 A.

"Deterswetting" (STW) These compositions include the different types of softening product during washing granulates or liquids (see, for example, EP 753,569 A, US 4,140,641, US 4,639,321, US 4,751, 008, EP 315,126, US 4,844,821; 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 that include conditioner cleaners. " 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 embedded devices. on 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 752,469 A); types of liquid detergent for fine fabrics, especially the variety of high foaming; rinse aid for dishwashing; liquid whiteners including both chlorine type and oxygenated bleach type, and disinfecting agents, mouth rinses, denture cleaners (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) 96/37595 A, WO 96/37592 A, WO 96/37591 A, WO 96/37589 A, WO 96/37588 A, GB 2,297,975 A, GB 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-fading 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 process can be integrated with current LAB manufacturing processes or with conventional linear detergent alcohol processes in any convenient manner. For example, a conventional erected plant can be changed to produce the modified modified alkylbenzenes and / or primary OXO alcohols in their entirety. Alternatively, depending on the desired volumes of available supply materials, for example as effluents from the LAB process or conventional linear detergent alcohol process or based on the proximity of sources of supply material from the petrochemical industry, a plant for the manufacture of the present modified alkylbenzenes and / or OXO alcohols modified primary 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. In an add-on mode, the present invention encompasses vinylidene olefin processing steps and from vinylidenolefin, modified alkylbenzene or alkyltoluene and / or modified primary OXO alcohol using the steps described in detail hereinbefore. The modified alkylbenzene or alkyltoluene is combined in a ratio of from about 1: 100 to 100: 1, more typically from about 1: 10 to about 10: 1, for example about 1: 5 in a conventional linear alkylbenzene, for example an alkylbenzene of C11.8 on average or any alkylbenzene produced by the DETAL® process. The mixture is then sulfonated, neutralized and incorporated into consumer cleaning product compositions. Parallel process steps or alternate process steps lead to modified primary OXO alcohol 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 a method utilizing the essential teachings of the present process . The present teachings, especially with respect to the de-linearization method, are believed to be reapplicable, for example, to the manufacture of modified alkyl sulfates and other surfactants.

EXAMPLE 1 Modified alkylbenzene sulfonate prepared by hydrocarbon-containing feedstocks obtained from effluent from MOLEX® with separation on SAPO-11, dehydrogenation using standard UOP method, alkylation on H-mordenite, sulfonation using sulfur trioxide / air; and Neutralization An appropriate feedstock is obtained in the form of a jet / diesel distillation portion from kerosene. This feedstock contains branched and linear paraffinic hydrocarbons, in which the linear hydrocarbons are of chain length suitable for LAB manufacture and in which the branched hydrocarbons include at least 10% branched paraffins with methyl, together with cyclic, aromatic hydrocarbons and other impurities. This flow is continuously passed to two adsorptive separation units, connected as shown in Figure 8 and Figure 1 in which the AC1 unit of Figure 8 in detail is charged with 5 Angstroms calcium zeolite as used in the conventional linear alkylbenzene manufacture and the AC2 unit of FIG. 8 in detail is charged with the silicoaluminophosphate SAf O-11. The AC1 and AC2 units together with the associated rotary valve devices, refining columns and effluent columns (RC and EC) and condensers (shown as horizontal tanks not marked in Figure 8) and other means shown, although uniquely connected , are generally constructed in accordance with the units licensed and commercially available through UOP Corp. (MOLEX® units). The adsorbate (extract) from the adsorptive unit AC1 with Ca zeolite is rejected and the refined material is continuously passed to the second adsorptive separation unit AC2 containing SAPO-11. The flow enriched with branched compounds taken from the AC2 unit as adsorbate or extract is passed to a standard commercial dehydrogenation unit of the LAB process provided by UOP Corp. (PACOL® process) loaded with a standard LAB dehydrogenation catalyst (DeH 5® or DeH 7® or similar) belonging to UOP Corp. After dehydrogenation under conventional LAB manufacturing process conditions, the hydrocarbons are continuously passed to an alkylation unit which is normally conventional but is loaded with H-mordenite (ZEOCAT® FM 8/25 H) wherein the alkylation proceeds continuously at a temperature of about 200 ° C with discharge upon completion by at least 90%, that is, a conversion to the hydrocarbon feed (olefins) of at least 90% This produces a modified alkylbenzene.

In optional variations, the above procedure can be repeated except with discharge when reaching an < 8E / erson (olefin-based) to the desired modified alkylbenzene of at least about 80%. A paraffin recycling is obtained by distillation at the rear end of the alkylation unit 5 and recycling is done ipksar back to the dehydrogenator. The procedure up to this point includes the steps and fluxes of Figure 1. The modified alkylbenzene can be further purified by additional conventional distillation (such distillation steps are not shown in Figure 1). The distilled modified alkylbenzene mixture is sulfonated intermittently or continuously, in a remote installation if desired, using sulfur trioxide as the sulfonation agent. Details of the sulfonation using an appropriate mixture of sulfur trioxide / air are provided in US 3,427,342, Chemithon. The modified alkylbenzenesulfonic acid product from the previous step is neutralized with hydroxide Sodium to give the modified alkyl benzene sulfonate mixture, sodium salt.

EXAMPLE 2 Modified alkylbenzene sulfonate prepared by material feed obtained from MOLEX® effluent, separation on SAPO-11, dehydrogenation using standard UOP method, alkylation on H-mordenite, sulfonation using sulfur trioxide / air, and neutralization An appropriate supply material is obtained in the form of an effluent or refined material from a LAB plant, specifically from the MOLEX® process unit of said plant. This refined material contains a high proportion of branched paraffinic hydrocarbons together with cyclic hydrocarbons, aromatics and other undesirable impurities. This refined material is continuously passed to an adsorptive separation unit constructed in a conventional manner, for example following the manner of a MOLEX® unit, but having a load of SAPO-11. This unit works under conditions generally similar to the MOLEX® unit as used in the manufacture of linear alkylbenzene and resembles the AC2 unit described in example 1. The refined or effluent material from the adsorptive unit with SAPO-11 is rejected and the adsorbate or extract which now meets the definition of the invention of a flow enriched with branched compounds is continuously passed to a standard commercial dehydrogenation unit of the LAB process provided by UOP Corp. (PACOL® process) loaded with a LAB dehydrogenation catalyst. standard (for example DeH 7®) belonging to UOP Corp. After dehydrogenation under conventional LAB process manufacturing conditions, the hydrocarbons are continuously passed to an alkylation unit which is normally conventional but is loaded with H-mordenite ( ZEOCAT® FM 8/25 H) where the alkylation proceeds continuously to a tea temperature of about 200 ° C with discharge upon reaching a pof alkylating agent conversion of at least about 90%. The modified alkylbenzene mixture is purified by conventional distillation and the branched paraffins are recycled to the dehydrogenation unit. The steps in the process up to this point follow Figure 4. The distilled modified alkylbenzene mixture produced in the process to this point is sulfonated intermittently or continuously, in a remote facility if desired, using sulfur trioxide as the agent of sulfonation. Details of the sulfonation using an appropriate mixture of sulfur trioxide / air are provided in US 3,427,342, Chemithon. The modified alkylbenzenesulfonic acid product from the previous step is neutralized with sodium hydroxide to give the modified alkyl benzene sulfonate mixture, sodium salt.

EXAMPLE 3 Modified alkylbenzene sulphonate prepared by feed material obtained from MOLEX® effluent, separation on pyrolyzed poly (vinylidene chloride), dehydrogenation using the standard UOP method, alkylation on H-ZSM-12, sulfonation using sulfur trioxide / air and neutralization. obtains an appropriate supply material in the form of a refined material from a LAB plant, specifically from the MOLEX® process unit of said plant. This refined material contains branched paraffinic hydrocarbons together with cyclic hydrocarbons, aromatics and other undesirable impurities. This refined material is passed continuously to an adsorptive separation unit 5 constructed in a conventional manner, for example of the MOLEX® type, not being conventionally incorporated into the design of a LAB plant and hereinafter referred to as the "SARÁN® unit". having a charge of pyrolyzed poly (vinylidene chloride), sieve diameter > 5 Angstroms, manufactured in accordance with the Netherlands NL Application 7111508, published on October 25, 1975. The "SARÁN unit" works under conditions generally similar to the MOLEX® unit. The refined material from the "SARAN unit" is rejected and the adsorbate is continually passed to a standard commercial dehydrogenation unit of the LAB process provided by UOP Corp. (PACOL® process) loaded with a standard LAB dehydrogenation catalyst such as DeH 7® belonging to UOP Corp. After dehydrogenation under conventional process LAB manufacturing conditions, the hydrocarbons are continuously passed to an alkylation unit which is normally conventional but is charged with H-ZSM 12 where the Alkylation proceeds continuously at a temperature of about 200 ° C with discharge upon reaching a feed hydrocarbon conversion of at least about 90%. The modified alkyl benzene mixture produced in the previous step is distilled and && * * M > % & & sulfone intermittently or continuously using sulfur trioxide as the sulfonation agent. Details of the sulfonation using an appropriate mixture of sulfur trioxide / air are provided in US 3,427,342, Chemithon. The modified alkylbenzenesulfonic acid product from the previous step is neutralized with sodium hydroxide to give the modified alkyl benzene sulfonate mixture, sodium salt.

EXAMPLE 4 Modified alkylbenzene sulfonate prepared by feedstock from urea clathrate formation; separation on SAPO-11, dehydrogenation using Pt catalyst, alkylation on zeolite beta acid, sulfonation using sulfur trioxide / air and neutralization An appropriate supply material is obtained from kerosene by formation of clathrates with urea which is used to remove a fraction rich in the most commercially valuable linear hydrocarbons. See US 3,506,569. The low grade branched effluent from the urea clathrate formation step is a hydrocarbon-based feedstock suitable for the present process. Any activating solvent such as methanol, if present, is removed therefrom and continuously passed to an adsorptive separation unit constructed in any conventional manner, for example rttßÜ? Uft. -i "«. »- -. zz fcJ ^ M9l» iU »go ^ a < at-- Ía ^, a ^ i > J ^ taA & ¿^ ^ & fej» ^. tzSlfz,? 8ty L * + and am »*? & u tß- following the mode of the MOLEX® processing units, but loaded differently, having a load of SAPO-11 The SAPO-11 unit works, under conditions similar to a standard MOLEX® processing unit Refined material from the SAPO-11 is rejected and the adsorbate is continually passed to a standard commercial dehydrogenation unit of the LAB process provided by UOP Corp. (PACOL® process) loaded with a catalyst dehydrogenation of non-branded platinum After dehydrogenation under conventional LAB manufacturing process conditions, the hydrocarbons are continuously passed to an alkylation unit which is normally conventional but is charged with Zeocat PB / H® where the alkylation proceeds continuously at a temperature of approximately 200 ° C with discharge when reaching a conversion of the hydrocarbon feed of at least approximately 90%. The modified alkylbenzene mixture produced in the previous step is sulfonated intermittently or continuously using sulfur trioxide as the sulfonation agent. Details of the sulfonation using an appropriate mixture of sulfur trioxide / air are provided in US 3,427,342, Chemithon. The modified alkylbenzenesulfonic acid product from the previous step is neutralized with sodium hydroxide to give the modified alkyl benzene sulfonate mixture, sodium salt. ^^^^^^^^^^^^^^^^^^^ i ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Modified alkylbenzene sulfonate prepared by hydrocarbon-based feedstock from kerosene 5 fraction from a highly paraffinic petroleum source, separation on grafted non-acidic zeolite, dehydrogenation using DeH 9® catalyst, alkylation on H-mordenite, sulfonation using acid chlorosulfonic and neutralization A jet / kerosene fraction is taken from a low viscosity crude oil, for example light Brent. This is continuously passed to an adsorptive separation unit constructed in any conventional way, for example following the mode of the MOLEX® processing units., but charged differently, having a grafted zeolite filler prepared in accordance with US 15 5,326,928. The unit works under conditions similar to a conventionally charged MOLEX® unit. The refined material from this unit is rejected and the adsorbate is continuously passed to a standard commercial dehydrogenation unit of the LAB process provided by UOP Corp. (PACOL® process) loaded with a standard LAB dehydrogenation catalyst DeH 9® belonging to UOP Corp. After dehydrogenation under conventional process LAB manufacturing conditions, the hydrocarbons are continuously passed to an alkylation unit which is normally conventional but is charged «FajafefeS»: 1, > - + yi «i & Ziiyiy- ¡- .----.,, ... -. • z- .l. .z. -My -.'.- ¿á! Á with H-mordenite (ZEOCAT FM 8/25 H) where the alkylation proceeds continuously at a temperature of about 200 ° C with discharge when reaching a conversion of the hydrocarbon fed of at least about 90%. The modified alkylbenzene mixture produced in the previous step is sulfonated intermittently or continuously using sulfur trioxide as the sulfonation agent. Details of the sulfonation using an appropriate mixture of sulfur trioxide / air are provided in US 3,427,342, Chemithon. The modified alkylbenzenesulfonic acid product from the previous step is neutralized with sodium hydroxide to give the modified alkyl benzene sulfonate mixture, sodium salt.

EXAMPLE 6 Compositions for cleaning product % by weight of sodium salt of modified alkylbenzenesulfonate is combined, which is the product of any of the above exemplified procedures with 90% by weight of a compact, agglomerated laundry detergent granulate.

AXIS 7 Compositions for cleaning product In this example, the following abbreviation is used for a modified alkylbenzene sulfonate, sodium salt form or potassium salt form, prepared according to any of the above process examples: MAS The following abbreviations are used for the auxiliary materials of products cleaning: Oxide of amine Cxy N-oxide of alkyldimethylamine RN (O) Me2 of given chain length wherein the average scale of total carbons of the portion R of alkyl not of methyl is from 10 + x to 10 + y. Amylase: Amylolytic enzyme, 60KNU / g activity, commercialized by NOVO Industries A / S under the trade name Termamyl® 60T. Alternatively, the amylase is selected from: Fungamyl (R), Duramyl (R), BAN (R); and enzymes of < x amylase described in WO95 / 26397 and co-pending application by Novo Nordisk PCT / DK96 / 00056. APA: C8-C10 amidopropyldimethylamine , > ^^ x s ^ < * & amp; - - * «Ois-s% 3fe ^ asH Cxy Betaine Alkyldimethylbetaine having an average total carbon scale of alkyl portion of 10 + x to 10 + y. Bicarbonate Baking soda, anhydrous, with a particle size distribution between 400μm -1200μm Borax Sodium tetrahydrate decahydrate BPP Butoxy-propoxy-propanol Brightener 1 4,4'-Bis (2-sulfoestyril) bifenyl disodium Brightener 2 4 , 4'-Bis (4-anilino-6-morpholino-1.3.5.-trizin-2-yl) amino) stilbene-2: 2'-disulfonate disodium CaCl2 Calcium Chloride Anhydrous Na2CO3 Carbonate, 200μm - 900μm Cellulase Cellulose Enzyme, 1000 CEVU / g, NOVO, Carezyme® Citrate trisodium citrate dihydrate, 86.4%, 425μm-850μm Citric acid Anhydrous citric acid CMC Sodium carboxymethylcellulose CxyAS Alkylsulfate, sodium salt another salt if specified, which has an average total carbon scale of alkyl portion of 10 + and 10 + and & $ & > * & amp; amp; & amp; & amp; * & amp; CxyEZ Linear or branched ethoxylated alcohol (which has no branching with methyl in the middle part of its chain) and which has an average total carbon scale of alkyl portion of 10 + y to 10 + y and an average of z moles of ethylene oxide. CxyEzS Alkylethoxysulfate sodium salt and having an average total carbon scale of alkyl portion of 10 + y to 10 + y and an average of z moles of ethylene oxide. (z moles of average ethylene oxide Diamine Alkyldiamine, for example, 1,3 propanediamine, Dytek EP, Dytek A, (Dupont), or selected from: dimethylaminopropylamine; 1,6-hexanediamine; 1,3-pentanediamine; methyl-diaminopropane; 1,3-cyclohexanediamine; 1,2-cyclohexanediamine Dimethicone Mixture of 40 (gum) / 60 (fluid) by weight of SE-76 dimethicone gum (GE Silicones Div.) / dimethicone fluid with a viscosity of 350 cS.

DTPA Acidtí ^ Ptilentriaminopentaacetic DTPMP Diethylenetriaminepenta (met? Lensphonate), Monsanto (Dequest 2060) Endolase Endoglucanase, activity 3000 CEVU / g, NOVO EtOH Ethanol Fatty acid (12/18) C12-C fatty acid 18 Fatty acid (12/14) C12-C14 fatty acid Fatty acid (14 / 18) Fatty acid of C14-C18 Fatty acid (RPS) Fatty acid of rapeseed Fatty acid (TPK) Fatty acid of palm seed Format Format (Sodium) HEDP acid 1, 1 -hydroxyethoxyphosphonic hydrotrope Selected sodium, potassium, magnesium salts , calcium, ammonium or water-soluble substituted ammonium of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylene-sulfonic acid. Isofol 12 Alcohol of Guerbet of X12 (average) (Condea) Isofol 16 Alcohol of Guerbet of C16 (average) (Condea) ^^^^^^^ g ^ ¡3g | gfe ^ fe &g The linear alkyl alkyl (C11.8, Na salt or Lipase Lipolytic Enzyme, 100kLU / g, NOVO, Lipolase®, alternatively, the lipase is selected from: Amano P; M1 Lipase (R), Lipomax (R); D96L lipolytic enzyme variant of the original lipase derived from strain Humicola laguginosa DSM 4106. LMFAA C12-C14 alkyl-N-methylglucamide LMFAA C12-C14 alkyl-N-methylglucamide MA / AA Maleic acid 1: 4 copolymer / Acrylic, sodium salt, average molecular weight 70,000.

MBAxEy Middle branched chain primary alkyl ethoxylate (average total carbons = x; average EO = y) MBAxEyS Modified primary or branched middle chain alkylcytosulfate, sodium salt (average total carbons = x; average EO = y) according to the invention ( see example 9). MBAyS Alkylsulfate branched primary in the medium chain, sodium salt (average total carbons = y) MEA Monoethanolamine MES Cxy Alkymethylmethersulfonate, sodium salt that has an average scale of total carbons of alkyl portion of 10 + x to 10 + y. MgCI2 Magnesium Chloride MnCAT Macrocyclic manganese bleach catalyst as in EP 544,440 A or, preferably, use [Mn (Bciclama) CI2] wherein 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 Cxy Paraffinsulfonate, sodium salt that has an average scale of total carbons of alkyl portion of 10 + x to 10 + y. NaSKS-6 Crystalline layered silicate of the formula d-Na2Si2O NaTS Sodium toluene sulfonate NOBS Nonanoyloxybenzenesulfonate, sodium salt LOBS C12 oxybenzenesulfonate, sodium salt PAA Polyacrylic acid (molecular weight = 4500) H PAE Tetra§Í &ethoxylated pentamine PAEC Methoxylated methyl ethoxylated dihexylenetriamine PB1 Anhydrous sodium perborate of nominal formula NaBO2.H2O2 PEG Polyethylene glycol (molecular weight = 4600) Percarbonate Sodium percarbonate, nominal formula 2Na2CO3.3H2O2 PG Propanediol Phthalocyanine bleach sulfonated zinc encapsulated in dextrin soluble polymer PIE Ethoxylated, hydrosoluble polyethylene imine Protease Proteolytic enzyme 4KNPU / g, NOVO; Savinase®; alternatively, the protease is selected from: Maxatase (R); Maxacal (R); Maxapem 15 (R); subtilisin BPN and BPN '; Protease B; Protease A; Protease D; Primasa (R); Durazym (R) QAS R2.N + (CH3) x ((C2H4O) and H) z with R2 = C8-C18 x + z = 3, x = 0 to 3, z = 0 to 3, y = 1 to 15. SAS Cxy Alkylsulfate secondary, sodium salt that has an average scale of total carbons of alkyl portion of 10 + x to 10 + y. 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; or, a combination of fumed silica and high viscosity polydimethylsiloxane (optionally chemically modified), non-aqueous solvent solvent, for example hexylene glycol, see also propylene glycol. SRP1 End blocked esters with sulfobenzoyl with oxyethyleneoxy base structure and terephthaloyl SRP2 Ethoxylated and sulphonated terephthalate polymer SRP3 Ethoxylated terephthalate polymer end blocked with methyl STPP Anhydrous sodium tripolyphosphate Sulfate Sodium sulfate, anhydrous TAED Tetraacetylethylenediamine TFA Alkyl N-methylglucamide of C16-18 • íibáß? S S Si? Á í ^ ßsmje ^ SJ? ^^ iéi ^ k & a ^ iSt? i ?.

Zeolite A Hydrated sodium aluminosilicate, Na12 (A102Si? 2) i2.27H2O; 0.1 -10μm Zeolite MAP Zeolite detergent grade (aluminum P maximum) (Crosfield) Typical ingredients often referred to as "minor" may include perfumes, dyes, pH cutters, etc. The following 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 F according to the invention were prepared: EXAMPLE 8 Product compositions for cleaning The following liquid laundry detergent compositions A to E were prepared according to the invention. The abbreviations are as they are used in the previous examples.

S ^ ^^^ M > ¿^ ^^^ í. ^ - ií '^ > - EXAMPLE 9 In the present example, a flow rich in hydrocarbon-based branched compounds is made and dehydrogenated, subjected to hydroformylation to make a modified, ethoxylated and sulfated primary OXO alcohol. A suitable unprocessed hydrocarbon feedstock is obtained in the form of a jet / diesel or kerosene distillation portion. This feedstock is low in sulfur, nitrogen and aromatics (to the extent that these are known to have some adverse effect on the life time of MOLEX ® and OLEX® adsorbent beds) and contain paraffinic and linear branched hydrocarbons, in which the linear hydrocarbons are of a chain length suitable for the manufacture of detergents and in which the branched hydrocarbons include at least 10% branched paraffins with methyl, together with cyclic hydrocarbons, aromatics and other impurities. The raw hydrocarbon feedstock is distilled to obtain a two carbon portion at approximately C14-C15. This forms a hydrocarbon-based feedstock for the remaining part of the process. See figure 10, flow 1. The distilled hydrocarbon feedstock is continuously passed to two adsorptive separation units, connected as shown in figure 10 in which the SOR 4/5 unit is . & »aft. - > - -r, ~ -? £ $ tiÉB & tK B ti Bß? Sti -, and *? aA to *? - £ yt-t, A »~« s * ***** loaded with Ca zeolite of 5 Angstrom as used in the manufacture of conventional linear alkylbenzene, and the SOR 5/7 unit is loaded with SAPO-11 silicoaluminophosphate. The general construction of the SOR 4/5 and SOR 5/7 units and of the auxiliary equipment that is not shown in Figure 10 is in accordance with concessionable units commercially available through UOP Corp. (MOLEX® units). The desorbent systems and the auxiliary recovery and distillation columns are not shown. The flux rich in linear compounds (flow 6 in Figure 10, rich in branched hydrocarbons) of the SOR 4/5 unit of MOLEX® with Ca zeolite is rejected and the flow rich in intermediate branched compounds (flow 2 in Figure 10, rich in branched hydrocarbons) is continuously passed to the second adsorptive separation SOR 5/7 unit containing the SAPO-11. The flow rich in branched compounds that was taken from the SOR 5/7 unit as adsorbate or extract (flow 3 in Figure 10, from more branched hydrocarbons) is passed to a standard dehydrogenation unit of the commercial LAB process (DEH in the 10) provided by UOP Corp. (PACOL® process) loaded with a standard dehydrogenation catalyst (DeH5® or DeH7® or similar) belonging to UOP Corp. After partial dehydrogenation (up to about 20%) under process preparation conditions of conventional LAB olefin feedstock, olefin / paraffin mixtures rich in branched compounds (flow 4 in Fig. 10) are continuously passed to DEFINE® and PEP® process units licensed from UOP Corp. These units hydrogenate the impurity of diolefin aromatic impurities, respectively. The resulting purified olefin / paraffin flow (54 in Figure 10) is now passed to a conferred OLEX® process unit, JOP Corp, loaded with olefin separation sorbent owned by oP Corp. After separation of olefins from the unreacted paraffins (the latter are recycled as flow 8 in Figure 10) are continuously passed to an OXO reaction unit operating at a 2-2.5: 1 ratio of H2: CO and using a pressure of 60-90 atm, and a temperature of approximately 170 ° C-210 ° C and which is charged with an organophosphine cobalt complex. The OXO proceeds continuously with discharge upon reaching a selectivity to the modified primary OXO alcohol of at least about 90%, and essentially all of the olefin in the feed stream has reacted. This produces a modified primary OXO alcohol according to the invention. As well a small amount of reduction occurs to form paraffin. The paraffins are separated by distillation and can be re-circulated to the dehydrogenator. The procedure up to this point includes the steps and fluxes of Figure 10. The modified primary OXO alcohol (flow 57 in Figure 10) is ethoxylated to an average content of one mole of ethylene oxide. The ethoxylation, propoxylation, etc. Alternates can be made using different amounts of alkylene oxide to produce the desired alkoxylate. This is done intermittently or continuously, in a remote installation if desired, using ethylene oxide and the usual base catalyst (see, Schonfeldt, Surface Active Ethylene Oxide Adducts, Pergamon Press, N.Y., 1969). The ethoxylated modified OXO alcohol is then treated intermittently or continuously with sulfur trioxide as sulfation agent (see "Sulphonation Technology in Detergent Industry", W. De Groot, Kluwer Academic Publishers, London, 1991). The product from the previous step is neutralized with sodium hydroxide to give modified alkyl ethoxysulfate, sodium salt, according to the invention. In variations of the previous example, the alkyl chain length of the hydrocarbon can be varied to produce the surfactants derived from the modified OXO alcohol of desired chain length as used in the formulation examples. In a further variation, the modified OXO alcohol can be sulfated without any previous alkylation.

EXAMPLE 10 A non-limiting example of non-aqueous liquid laundry detergent containing bleach having the composition as set out in the following table is prepared.

TABLE Component% by weight Scale (% by weight) Liquid phase LAS 25 0 18-35 C24E5 or MBA 14 3E5 (Ex 13 6 10-20 9) Solvent or hexylene glycol 27 3 20-30 Perfume 0 4 0-1 0 MBA 14 4E1S (Example 9) 2 3 1-3 0 Solid Phase Protease 0 4 0-1 0 Citrate 4 3 3-6 PBI 3 4 2-7 NOBS 8 0 2-12 Carbonate 13 9 5-20 DTPA 0 9 0-1 5 Brightener 0 4 0-0 6 Silicon antifoam 0 1 0-0 3 Minors 1 • this The resulting composition is an anhydrous liquid detergent for heavy-duty laundry that provides excellent stain and dirt removal performance when used in normal fabric washing operations.

Liquid detergent compositions are prepared according to the following.

It was discovered that liquid detergent compositions (A-D) are very efficient in removing a wide range of stains and dirt fabrics under various conditions of use.

EXAMPLE 12 • $ - The following compositions (E to J) are heavy-duty liquid laundry detergent compositions in accordance with the present invention.

EXAMPLE 13 A Water based heavy-duty laundry detergent compositions K to O comprising the branched surfactants in the middle part of their chain of the present invention are presented below.

* "! - EXAMPLE 14 The following aqueous liquid laundry detergent compositions P a T are prepared according to the invention.

EXAMPLE 15 Heavy duty liquid dishwashing detergent compositions comprising the modified primary OXO alcohol derived surfactants of the present invention were prepared.

The following laundry detergent compositions K to O were prepared according to the invention.

^ * ATTENTION- ^ EXAMPLE 17 The following laundry detergent compositions P a T repaired according to the invention. * t Ar & A EXAMPLE 18 The following high density detergent formulations U to X, were prepared according to the present invention.

The present process can utilize many hydrocarbon-based feedstocks, as already illustrated herein. Alternate hydrocarbon feedstocks that can be used in this procedure include mixtures of specific types of fc ^ paraffins and / or mono-olefin ^. These hydrocarbon grades can be selected from: A.- Paraffin mixtures according to the formula: R R1 R2 CH3 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) zCH3 In which the total number of carbon atoms in the portion The branched primary alkyl (including the branching R, R1 and R2) is from 8 to 20, preferably from 10 to 20, preferably from 10 to 18; R, R1 and R2 are each independently selected from hydrogen, C1-C3 alkyl, and mixtures thereof with minor proportions of impurities such as C3-C7 cycloalkyl, aryl, arylalkyl and alkaryl, preferably provided with H, and C 1 -C 3 alkyl (more preferably methyl), with the proviso that R, R 1 and R 2 are not all hydrogen and, when z is 0, at least R or R 1 is not hydrogen; w, x, y, z are each independently integers from 0 to 13, subject to the limitation of the total number of carbon atoms stated above and w + x + y + z is preferably from 8 to 14. 20 The paraffins which are most prefer to have only H, methyl, ethyl, propyl or butyl in R, R1 and R2, more preferably only H and methyl, with the proviso that R, R1 and R2 include at least one alkyl portion; and methyl, when present, is preferably internal, that is, eliminated as much as possible from positions 1-, 2-, and preferably up to 3- in the longest accounting chain. The hydrocarbons of the present also include: B.- Mixtures of mono-olefipas. Those mono-olefins are related with the paraffins of A above, in which any of the suitable mono-olefins can be made by dehydrogenation of any of the paraffins of A above. (In practice, suitable olefins can be isolated first, and then hydrogenated to paraffins). Preferred olefins are mono-olefins, although in general, up to 10% by weight of the olefinic hydrocarbon may be diolefins, after dehydrogenation of the appropriate paraffins. Like the paraffins, the olefins herein can vary widely in structure, for example, the possible mono-olefins are: These structures are of course illustrative and should not be considered as limiting. The hydrocarbons herein also encompass: C- Mixtures of the paraffins of A and the olefins of B. Those mixtures of hydrocarbons herein can be any possible combination, and may be, for example, the result of combining compositions containing only paraffins, only olefins, or mixtures of paraffins / olefins in any proportion. Mixtures can be derived "inherently" as a consequence of the hydrocarbon that comes from a natural source, for example, raw material of geologically extracted petroleum (for example, light crude or kerosene or jet / diesel fuels distilled thereof) , typically with some treatment of said material (for example, by fraction formation, selective sorption, distillation, clathrate formation, etc.) to isolate the preferred hydrocarbon mixtures. Alternatively, the mixtures can be formed by progressively mixing more complex mixtures from a series of hydrocarbons of simpler composition. The hydrocarbon mixtures herein are also derived from a known synthetic transformation in petroleum chemistry, for example, thermal decomposition, thermal hydrodecomposition, hydroisomerization, hydrogenation, dimerization, dehydrogenation, isomerization, disproportionation, and the like. In addition, equivalent compositions can be formed in a more arduous manner by means of known organic synthetic schemes, for example those involving Grignard reactions. Catalytic isomerizations on zeolites and modified zeolites may be particularly useful. Mixtures of hydrocarbons useful herein may further include: Safes Mixtures of A-D paraffin with benzene or other non-aliphatic hydrocarbons. This includes the use of other solvents such as cyclohexane, pentene, toluene, etc. A group of preferred paraffins has the formula selected from: CH3 CH3 (CH2) aCH (CH2) bCH3 (II) Or mixtures thereof, in which a, b, d, and e are integers, a + b is from 10 to 16, d + e is from 8 to 14 and in which also when a + b = 10, a is an integer from 2 to 5 and b is an integer from 5 to 8, when a + b = 11, a is an integer from 2 to 5 and b is an integer from 6 to 9, when a + b = 12, a is an integer from 2 to 6 and b is an integer of 6 a , when a + b = 13, a is an integer from 2 to 6 and b is an integer of 7 a 11, when a + b = 14, a is an integer from 2 to 7 and b is an integer from 7 to 12, when a + b = 15, a is an integer from 2 to 7 and b is an integer from 8 to «* 13, when a + b = 16, a is an integer from 2 to 8 and b is an integer of 8 a 14, when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6, when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7, when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8, when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9, when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to , when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 1 1, when d + e = 14, d is an integer from 2 to 13 and is an integer from 1 to 12. The hydrocarbon compositions herein can accommodate varying amounts of impurities (say up to 20%, preferably below about 1%), such as impurities in which one or more oxygen atoms of ether or alcohol are present or interrupt the carbon chain (so-called "oxygenated" impurities); or impurities in which portions such as aryl, arylalkyl or alkaryl are attached to the carbon chain as the branches, or impurities in which quaternary carbon atoms, or diolefins, or impurities are present in which non-hydrogen portions are adhered to adjacent carbon atoms. Said impurities are of course unwanted. It is especially preferred to limit any impurities that are known to adversely affect biodegradation or produce unpleasant odors. For a larger mass efficiency, a minimum of the total carbon content is placed in any of the side chains, with the proviso that the resulting hydrocarbon still preferably has at least one carbon atom in a side chain. The paraffins and / or olefins which are preferred herein may contain varying amounts of non-aromatic alkylbenzene, cycloalkyl and alkylcycloalkyl impurities, although these are more desirably removed, for example by sorption steps. The paraffins and / or olefins which are preferred herein may contain some sulfur and / or nitrogen, but these may produce objectionable flavors and for this or other reasons are preferably removed by any well-known desulfurization and / or nitrogen elimination technique. in the oil industry. Preferred olefins are closely related to the above paraffins: they have structures that are formed by dehydrogenation of any of the paraffins at any accessible position to form the corresponding mono-olefin. Olefins which are particularly preferred are branched with monomethyl and branched with dimethyl, in particular branched with monomethyl.

It should be understood and appreciated that the underlying concept taught in respect to how to select preferred paraffins and olefins for best results herein involves several features including: Making a deliberate selection of hydrocarbon mixtures of 5 C 10 -C 18 having typically one or two alkyl substituents, these preferably being as short as possible, and being placed in at least one manner consistent with avoids problems of biodegradation. In this way, the hydrocarbons herein clearly differ substantially from the type of tetrapropylene which is highly non-biodegradable; and preferably having at least some methyl portions that are not in the 2- position of the longest hydrocarbon chain. Without pretending to be limited by theory, it is believed that some of the most complex mixtures within the defined scales have especially superior characteristics for hydrophobic formation for "modified" surfactants, highly soluble, resistant to hardness, that tolerate cold water including alkylbenzenes and oxo alcohols. Additionally, these hydrocarbon mixtures can be widely used in the production of modified surfactants. They can be used to prepare the modified alkyl sulfates, alkylalkoxylates, alkylalkoxy sulfates or alkylarylsulfonates, such as alkylbenzene sulphonates. The alkyl sulphates, alkylalkoxylates, alkylalkoxy sulfates are prepared by first converting the hydrocarbon mixtures to the corresponding alcohol and then optionally sulfating and / or alkoxylating the ^ ^^^^^^ ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^ ** ^ alcohol. The alcohol can be formed by any conventional means, such as the oxo process. And similarly sulfation and / or alkoxylation may be by conventional means. The alkylbenzene sulfonates are formed by alkylation of benzene with hydrocarbon mixtures containing olefinic compounds and then sulfonation of the resulting alkylbenzene. The alkylbenzene sulphonates formed are so-called "modified alkylbenzene sulphonates". ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^

Claims (24)

NOVELTY OF THE INVENTION CLAIMS

1. - A method comprising: (a) at least one step of at least partially separating a hydrocarbon-based feedstock comprising branched aliphatic hydrocarbons having from 8 to 20 carbon atoms in at least one flux rich in Branched compounds comprising an increased proportion of branched non-cyclic hydrocarbons in relation to the hydrocarbon-based feedstock and optionally, one or more of: a flux rich in linear compounds comprising an increased proportion of branched non-cyclic hydrocarbons in relation to the material of hydrocarbon-based food; and a flow of reject material comprising cyclic and / or aromatic hydrocarbons and / or branched with ethyl and / or higher; wherein said step (A) comprises: supplying said hydrocarbon-based feedstock and adsorptive separation of the feedstock in flows using porous media, said step (A) utilizing adsorptive separation means of simulated movement bed comprising: at least one honeycomb containing the porous medium; and a device for simulating movement of the porous medium in the opposite direction to a flow of hydrocarbons in said bed; (B) (i) dehydrogenate at least partially the flow rich in branched compounds from step (A) thus forming a flux rich in compounds olefinic branching comprising mono-olefin, optionally followed by one or more of (ii) treating said flux rich in olefinic branched compounds to decrease the diolefin impurities therein and (iii) treating said flux rich in olefinic branched compounds to decrease in the same aromatic impurities; (C) optionally, partially concentrating the mono-olefins in the olefinic branched-chain rich stream of step (B) by adsorptive separation means using a known solvent or porous medium with the proviso that said solvent or porous medium does not are identical with the porous medium of step (A) and are adapted for olefin / paraffin separations and, optionally, concurrently recirculating the paraffins to said dehydrogenation step (B); and (D) reacting said flux rich in olefinic branched compounds produced in step (B) or, optionally, as further concentrated in step (C), with carbon monoxide and hydrogen in the presence of an OXO catalyst, forming thus a modified primary OXO alcohol.

2. A method according to claim 1 that meets at least one of the following requirements: the means of step (A) comprise one, two or more of said devices and at least two beds, at least one of the beds comprises the porous medium with content other than the content of the porous medium of another of the beds by an increased capacity to reneter non-cyclic aliphatic hydrocarbons branched with methyl; and stage (D) is an OXO stage of a step in which ÍS *. The OXO catalyst is a transition metal coordinated with phosphine other than iron.

3. A process according to claim 2 further characterized in that at least one of the beds comprises conventional porous medium for the manufacture of linear alkylbenzenes for the manufacture of linear alkylbenzenes; said at least one bed being connected in said method in a suitable manner with the at least partial increase in the proportion of branched non-cyclic aliphatic hydrocarbons with methyl in the flows going to stage (B) of said process, and suitable with the at least partial decrease in the proportion of linear non-cyclic aliphatic hydrocarbons passing to step (B) of said process, said linear non-cyclic aliphatic hydrocarbons being removed at least partially as a flux rich in linear compounds in said step ( to).

4. A method according to claim 3, further characterized in that the adsorptive separation means with simulated movement bed in step (A) comprise; one of said devices, with the proviso that said device is capable of simulating the movement of the porous means in at least two of at least one bed; or at least two of said devices.

5. A method according to any of claim 4, further characterized in that there are two said at least one bed, each containing a different element of said porous means, each of said at least one bed being controlled by one of said devices, and each of said devices having a minimum of eight ports to achieve the simulated movement of the porous medium in said at least one bed.

6. A method according to claim 4, further characterized in that said flux enriched with linear compounds is present in step (A) and said step (A) comprises: (Ai) adsorptive separation of the hydrocarbon-based feedstock in said flux enriched with linear compounds and an intermediate flow rich in branched compounds and the rejection of the flux enriched with linear compounds by means of one of said adsorptive separation means with simulated movement bed; followed by (A-ii) adsorptive separation of said intermediate flow rich in branched compounds in flux enriched with branched compounds comprising an increased proportion of branched non-cyclic aliphatic hydrocarbons relative to the intermediate flow rich in branched compounds, and said flow of rejection comprises at least an increased proportion of cyclic and / or aromatic hydrocarbons relative to said flow enriched with branched compounds, by means of another of said adsorptive separation means with simulated movement bed.

7. A process according to claim 2, further characterized in that all the beds comprise porous medium that is not conventional for the manufacture of linear alkylbenzenes; saying ki ^ > The porous medium has suitable pore sizes for, and being connected in said process, in a manner consistent with at least partially increasing the proportion of linear and / or branched non-cyclic aliphatic hydrocarbons with methyl in flows passing to the stage. (B) of the process, and at least partially reduce the proportion of aliphatic, cyclic, aromatic and / or branched hydrocarbons with ethyl or higher branching to process step (B), said hydrocarbons different from methyl and branched hydrocarbons; linear ones being eliminated at least partially in stage (A).

8. A process according to claim 3, further characterized in that the hydrocarbon-based feedstock comprises at least 10% branched paraffins with methyl having a molecular weight of 128 and no more than 282.

9.- A process according to claim 3, further characterized in that a distillation step is present before step (D), wherein said distillation process produces a narrow portion of no more than three carbon atoms (preferably no more than two carbon atoms) on the scale of C10 to C17 in the flow rich in olefinic branched compounds.

10. A process according to claim 9, further characterized in that the hydrocarbon-based feedstock or the olefinic branched-chain-rich stream is subjected to said distillation step.

11. - A process according to claim 3, further characterized in that the hydrocarbon-based feedstock is a refined material by adsorptive separation which is derived from a linear alkylbenzene manufacturing process or conventional linear detergent alcohol process.

12. A method according to claim 3, having the additional step or steps in sequence that are selected from: (E) sulfatar and neutralize the product of step (D); (F) alkoxylating the product of step (D); and (G) alkoxylating, sulfating and neutralizing the product of step (D).

13. A method according to claim 12 having the additional step of (H) mixing the product of the preceding steps with one or more adjunct materials for cleaning product; thus forming a cleaning product.

14.- Modified primary OXO alcohol produced by a process according to claim 1.

15. The consumer cleaning product containing a surfactant produced by a process according to claim 12 followed by a step of mixing the minus an attached ingredient for cleaning product.

16. A process according to claim 1, further characterized in that before said OXO step (D), the product of step (B) or (C) is mixed with a conventional detergent olefin.

17. - A method according to claim 13, further characterized in that the product of any of the subsequent steps (E), (F) or (G) is mixed with a conventional detersive surfactant.

18. A method according to claim 1, further characterized in that it additionally comprises at least one step of reacting the product of step (B) with an aromatic hydrocarbon selected from the group consisting of benzene, toluene and mixtures thereof. in the presence of an alkylation catalyst.

19. A method according to claim 18, further characterized in that said alkylation catalyst has a selectivity towards the internal isomer from 0 to 40.

20. A process according to claim 18, further characterized in that means are provided for direct the product from step (C) to stage (D), or to the alkylation step, or to both stages in parallel.

21. The product according to claim 12.

22. A detergent or cleaning composition comprising: (a) an effective amount of a detersive surfactant selected from alkyl sulfates, alkylpoly (alkoxy) sulphates, alkylpoly (alkoxylates) and mixtures thereof, said surfactant incorporates the radical RO- of a detergent alcohol of R = C9-C20 of formula ROH, in which R is mixtures of branched chains with methyl and some linear and said alcohol is further characterized in that it comprises the product of at least one Fischer-Tropsch process step or a stage of oligomerization or dimerization or isomerization of structure or stage of provision of paraffin, at least one stage of procedure OXO; with the proviso that in at least one step prior to the OXO process step an adsorptive separation step is present which has the effect of increasing the proportion of branched olefin with methyl which is used as feed material in said process step OXO; and (b) one or more adjunct materials that contribute at least partially to the useful properties of the composition.

23. A cleaning or detergent composition according to claim 22, further characterized in that R is selected from mixtures of branched chains with medium chain and some linear methyl chains.

24. A detergent or cleaning composition comprising: (a) an effective amount of a detersive surfactant which is selected from alkyl sulphates, alkyl poly (alkoxy) sulfates, alkyl poly (alkoxylates) and mixtures thereof, said surface active agent incorporating radical RO- of a detergent alcohol of R = C9-C20 of formula ROH, in which R is mixtures of branched chains with methyl and some linear and said alcohol is further characterized in that it comprises the product of a process according to the claim 1; and (b) one or more adjunct materials that contribute at least partially to the useful properties of the composition.