KR20040053249A - Improved processes for making alkylbenzenes via adsorptive separation and products thereof - Google Patents

Abstract

The present invention relates to a process for preparing particularly branched, more particularly monomethyl-branched or not co-carbon-based surfactants for use in cleaning articles; Preferred methods include specific combinations of two or more adsorptive separation steps, more preferably specific OXO and / or alkylation steps; Products by this method include certain modified primary OXO alcohols and / or alkylbenzenes, modified primary OXO alcohol-derived alkoxylated alcohols, alkylsulfates and / or alkoxysulfates, alkylbenzenesulfonate surfactants, and these Containing consumable cleaning products, in particular laundry detergents. Preferred methods herein, in particular, to obtain certain branched hydrocarbon distillates used in further processing steps to prepare olefins useful in the OXO process or as alkylating agents for the production of arenes or other useful surfactants. An unusual sequence of adsorptive separation steps is used. Surprisingly, such distillates can also be derived from effluents in current linear alkylbenzene preparations.

Description

Improved processes for making alkylbenzenes via adsorptive separation and products etc.

The present invention belongs to the field of preparation of surfactants useful in cleaning articles. Preferred methods include particular combinations of special adsorptive separation steps that separate particular hydrocarbons using specific means. Preferably, the means is a combination of two or more special adsorbent beds and two or more special types of rotary valves, as well as certain types of porous adsorbents with larger pore sizes than those used in conventional linear alkylbenzene preparations. It includes. In addition, preferred methods use specific alkylation steps with specific internal isomer selectivity. The present invention is also prepared by the process, including certain modified alkylbenzenes, modified alkylbenzenesulfonate surfactants, detergent alcohols and surfactants derived therefrom, and consumable cleaning articles, especially laundry detergents containing them. Belongs to the product field. Preferred methods herein utilize a non-conventional sequence of adsorptive separation steps to obtain certain branched hydrocarbon distillates, which are then further processed as alkylating agents for the preparation of arene or other useful surfactants, for example , OXO reaction to form certain detergent alcohols, followed by alkoxylation, sulfated and the like. Surprisingly, this distillate may also be derived from the effluent in current linear alkylbenzene preparations.

Background of the Invention

Historically, highly branched alkylbenzenesulfonate surfactants such as alkylbenzenesulfonate surfactants (known as "ABS" or "TPBS") based on tetrapropylene have been used in detergents. However, they have been found to be very poor in biodegradability. By making the alkylbenzenesulfonates as practically as linear as possible (“LAS”), it took a long time to improve their preparation. The large-scale production of linear alkylbenzenesulfonate surfactants is overwhelmingly aimed at this. The large scale commercial alkylbenzenesulfonate process used in the United States today is for linear alkylbenzenesulfonates. However, there are also limitations on linear alkylbenzenesulfonates; For example, it would be more desirable if they could improve hard water cleaning properties.

In the petroleum industry, a method has recently been developed for producing, for example, low viscosity lubricating oil or high octane gasoline, which provides the inventors with new insights into how to delinearize hydrocarbons to a limited and controlled degree. It turned out. However, this intended delinearization is not a feature of all recent commercial processes in other fields of preparing alkylbenzenesulfonate surfactants for consumer products. This is not surprising in view of the majority of literature in the field of LAS surfactants that the teaching of delinearization disappears and teaches ubiquitous in linear compounds.

Most commercial methods of preparing alkylbenzenes rely on the alkylation of HF or aluminum chloride catalyzed benzene. It has recently been found that certain zeolite catalysts can be used to alkylate benzene to olefins. Such process steps are described in the literature for other conventional methods of preparing linear alkylbenzenesulfonates. For example, zeolite alkylation catalysts are used in the DETAL ^R process of UOP. The DETAL ^R process and all other current methods of commercially preparing alkylbenzenesulfonates are considered to be inconsistent with the preferred methods of the present invention and the conditions for the internal isomer selectivity of alkylation catalysts, as defined below. In addition, the catalyst of the DETAL ^R process is considered to be lacking in terms of the mild acidity and intermediate pore size that the alkylation catalyst used in the preferred process of the present invention should have. Other recent documents describe the use of mordenite as an alkylation catalyst, but these documents do not combine the specific process steps required by the present invention. In addition, in terms of the preferred linearity in alkylbenzenesulfonate products prepared by commonly known methods, they also generally comprise the steps of providing or preparing a substantially linear hydrocarbon, rather than a delinearized hydrocarbon, prior to alkylation. do. Possible exceptions are in US Pat. No. 5,026,933 and US Pat. No. 4,990,718. These and other known processes limit the cost, catalyst limitations in the propylene oligomerization or olefin dimerization step, the presence of large amounts of distillate that may need to be discarded or may provide a non-consumable cleaning article, and obtainable chain lengths. There are a number of disadvantages in the detergent industry in the limited range of product compositions comprising mixtures with In summary, this development by the petroleum industry is not the best from the point of view of professional cleaning products manufacturers.

It is also known in the art to prepare linear alkylbenzenes using special adsorptive separation processes (see US Pat. No. 2,985,589). However, the process as described so far does not provide branched alkylbenzenesulfonates.

It is also known in the art to prepare long chain methyl paraffins for use as industrial solvents by methods comprising urea clathration and separation on “molecular sieves” [Chemical Abstracts] , 83: 100693 and JP 49046124 B4. The process involves a dual urea, such as treating the petroleum distillate once with urea to remove n-alkanes as complexes, and then secondly with excess urea to obtain adducts of mixed n-alkanes and long-chain monomethyl paraffins. Includes additive reactions absolutely. The method may be included in the overall method of the present invention, which has some limited utility and is mostly broadly defined, but it is quite limited. Although this method was published in 1974, it is known that it has not been used in the overall process for preparing surfactants, such as the modified alkylbenzenesulfonates described herein.

As further described in the background section below, methods for preparing various OXO alcohols and methods for preparing surfactants therefrom are also known. However, currently available OXO alcohols rely on relatively expensive processes such as olefin oligomerization, isomerization and disproportionation to prepare surfactants that are less soluble at a given chain length than may be required for the low laundering temperatures at which daily spread. That; Or a disadvantage that the content of the linear substance is still relatively high.

WO 97/39090, WO 97/39087, WO 97/39088, WO 97/39091, WO 98/23712, WO 97/38972, WO 97/39089, US Pat. No. 2,985,589; Chemical Abstracts, 83: 100693; JP 49046124 B4 (12/07/74); EP 803,561 A2 (10/29/97), EP 559,510 A (9/8/93); EP 559,510 B1 (1/24/96); US Patent No. 5,026,933; US Patent No. 4,990,718; US Patent No. 4,301,316; US Patent No. 4,301,317; US Patent No. 4,855,527; U.S. Patent 4,870,038; US Patent No. 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 Patent No. 2,564,072; US Patent No. 3,196,174; US Patent No. 3,238,249; US Patent No. 3,355,484; US Patent No. 3,442,964; US Patent No. 3,492,364; US Patent No. 4,959,491; WO 88/07030 (9/25/90); U.S. Patent 4,962,256; US Patent No. 5,196,624; US Patent No. 5,196,625; EP 364,012 B (2/15/90); US Patent No. 3,312,745; US Patent No. 3,341,614; US Patent No. 3,442,965; US Patent No. 3,674,885; US Patent No. 4,447,664; U.S. Patent 4,533,651; US Patent No. 4,587,374; US Patent No. 4,996,386; US Patent No. 5,210,060; US Patent No. 5,510,306; WO 95/17961 (7/6/95); WO 95/18084; US Patent No. 5,510,306; US Patent No. 5,087,788; US Patent No. 4,301,316; US Patent No. 4,301,317; US Patent No. 4,855,527; U.S. Patent 4,870,038; US Patent No. 5,026,933; US Patent No. 5,625,105; And US Pat. No. 4,973,788 are useful in the context of the present invention. The cited documents EP 559,510A and B are particularly concerned with producing gasoline with high octane values by recycling the stream to the isomerization reactor. Grafting of zeolites with tin alkyl and grafted porous materials of EP 559,510 is useful in the present invention. U.S. Pat.No. 5,107,052 also relates to improving the octane rating of gasoline and uses various molecular sieves such as AIPO4-5, SSZ-24, MgAPO-5 and / or MAPSO-5 containing less than 2% moisture. To separate C4-C6 methyl paraffins. Such sieves can absolutely adsorb dimethyl paraffin selectively and not monomethyl and normal paraffin.

Recently, methods for preparing alkylbenzenesulfonate surfactants have been reviewed. Vol. 56 in "Surfactant Science" series, Marcel Dekker, New York, 1996, especially Chapter 2 entitled "Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108. This operation gives access to a vast literature describing various processes and process steps such as dehydrogenation, alkylation, alkylbenzene distillation and the like. See, "Detergent Alkylate" in Encyclopedia of Chemical Processing and Design, Eds. McKetta and Cunningham, Marcel Dekker, NY, 1982., especially pages 266-284. Adsorption processes and other related processes, such as the Sorbex process of UOP, are also described in Kirk Othmer's Encyclopedia of Chemical Technology, 4 ^th . Edition, Vol. 1, "Adsorption and Liquid Separation", pages 583-598 and references cited therein; And publications by UOP Corporation, including the "Processing Guide" available from UOP Corporation (Des Plaines, Illinois). Commercial paraffin isolation and separation processes using molecular sieves include liquid phase processes MOLEX ^R (UOP Inc.) and gas phase processes ISOSIV ^R (Union Carbide Corp.), as well as ENSORB ^R (Exxon Corp.) and TSF ^R or Texaco Selective Finishing There is an optional machining process. All of these processes use 5mm molecular sieves as the porous medium. Although not described herein, operating temperatures, pressures, and other operating conditions and apparatus for any process step are common. That is, as is well known and defined in the literature for producing linear alkylbenzenesulfonate surfactants. The full text of references is cited herein.

US Patent No. 3,732,325, issued May 8, 1973, describes a process for the adsorptive separation of aromatic hydrocarbons.

US Patent No. 3,455,815, issued July 15, 1969, US Patent No. 3,291,726, issued December 13, 1966, US Patent No. 3,201,491, issued August 17, 1965, and May 23, 1961. US Pat. No. 2,985,589 to U.S. Patent No. 2,985,589 describes a simulated moving bed adsorptive separation for hydrocarbons.

U.S. Patent Nos. 5,780,694, issued July 14, 1998, and WO 98/23566, published June 4, 1998, disclose certain branched detergent alcohols and derivable surfactants therefrom. It is about. These documents include well known techniques of OXO processes and catalysts suitable for hydroformylation. See, in particular, columns 10 and 11 of patent '694.

U.S. Patent No. 5,510,564, issued April 23, 1996, incorporated herein by reference, describes a method for purifying hydrocarbons, particularly in connection with aromatic hydrocarbon removal.

US Patent No. 5,276,231, issued January 4, 1994, describes the removal of aromatic hydrocarbons from hydrocarbons by sulfolane extraction.

US Pat. No. 4,184,943, issued January 22, 1980, describes adsorption hydrocarbon separation.

US Patent No. 4,006,197, issued February 1, 1977, describes adsorption hydrocarbon separation of n-paraffins.

US Pat. No. 5,220,099, issued June 15, 1993 and US Pat. No. 5,171,923, issued December 15, 1992, purify paraffins by removal of aromatic, sulfur, nitrogen, and oxygen containing compounds, and magnesium Colorants by Y or Na-X zeolite adsorption are described.

See Surfactant Science Series, Volume 7, "Anionic Surfactants", Part 1, Marcel Dekker, N.Y., Ed. W. Linfield, 1976, Chapter 2, "Petroleum-Based Raw Materials for Anionic Surfactants", pages 11-86, provides a background that includes an overall background for OXO processes (pp. 71f) and specific feedstocks (pp. 60f). to provide. Attention, pp. Under the heading “side chain olefins” at 65f, the document does not describe suitable side chain olefins for use in the process of the present invention-the identified “side chain” olefins are of an incompatible type which are biologically “hard”. pp. A discussion of the OXO process at 72f suggests that linear olefins are converted to “branched” and mixtures of linear aldehydes and / or alcohols. In addition, the use of the term “branched” is different from the present invention—the method of the invention wherein the OXO reaction herein provides a specific methyl-branched primary alcohol due to the OXO reaction where only the minor aspect of the branching occurs. All include the use of a partially or entirely heavy chain methyl-branched feedstock as the main source of branching.

Individually, the literature immediately above and the references cited therein also describe UOP OLEX ^R processes and adsorbents useful herein [see, eg, pp. 60-63 mentions Cu- or Ag-doped zeolites. More particularly, for X- or Y-type zeolites doped with silver, see US Pat. No. 3,969,276, issued July 13, 1976. See also, DB Broughton and RC Berg, Hydrocarbon Process, Vol. 48 (6), 115 (1969); DB Broughton and RC Berg, National Petroleum Refiners Association, 1969 Annual Meeting, March 23, 1969, technical paper AM-69-38; DB Broughton and RC Berg, Chemical Engineering, January 26, 1970, page 86, article entitled "Two processes team up to make linear monoolefins"].

See Kirk Othmer's Encyclopedia of Chemical Technology, 4 ^th . Edition, Vol. 1, pages 893-913 (1991), article entitled "Alcohols, Higher Aliphatic", sub-heading "Synthetic Processes", especially "Modified CobaltCatalyst, One-Step, Low Pressure Process", at pages 904-906 An OXO reaction is described that forms Diagrams presenting methyl-branched alcohols (see, eg, pp. 904) are prepared entirely from linear precursors, and the OXO-branches are in the 2-position (as described in the literature identified above). Notice again.

See, for example, Surfactant Science Series, Volume 56, "Anionic Surfactants", Marcel Dekker, N.Y., Ed. W. Linfield, 1976, Chapter 1 "Raw Materials for Anionic Surfactant Synthesis", pages 1-142, and additional techniques for conventional feedstocks in detergent preparation, techniques of known methods for adsorption and other separation methods, See the description of detergent alkylation and the technology of the OXO or hydroformylation process step. See 23-25.

Literature on the OXO process is also described in "New Syntheses with Carbon Monoxide", Ed. J. Falbe, Springer-Verlag, New York, 1980].

Commercial practice of preparing detergent alcohols different from those available here typically involves the separation of linear paraffins from kerosene by adsorptive separation, dehydrogenation into linear internal olefins by PACOL ^R process (or similar process), Separating olefins from paraffins by an OLEX ^R process (or similar process), and in a manner to obtain 2-alkyl substituted primary alcohols, eg, LIAL ^R alcohols of ENI, by conventional OXO catalysts, or olefins Isomerized at the terminal position and then the OXO reaction step by one of the methods by terminal OXO addition.

See also WO 97/01521 A1 and 95 ZA-0005405, published January 16, 1997. In addition, various technical announcements and publications of the company are made, particularly with respect to known or available OXO alcohols, which are manufactured or manufactured by the patented OXO process in Sasol and / or Sastech of South Africa. See.

In a preferred embodiment, the present invention relates to a process for preparing modified alkylbenzenesulfonate surfactants, or modified primary OXO alcohols and surfactants derived therefrom, or combinations of these different surfactant types. These methods are disclosed from hydrocarbon feeds, which are defined in more detail elsewhere herein. "Modified" implies a very special type of branching. Specifically, for example, in connection with OXO alcohol herein, "modified" is substantially prevented from branching into a type that may have side effects on biodegradation or in locations that may have side effects on biodegradation, Methyl branched at a position other than the usual OXO position. Preferred "modified" means mono-lower alkyl at the heavy chain position of the OXO alcohol, in particular monomethyl substitution. The process comprises a particularly defined adsorptive separation step (a) and an alkylation step (c) when producing modified alkylbenzenes and / or alkylbenzenesulfonates. Among the utilities useful to detergent manufacturers, the hydrocarbon feed may be adsorptive raffinate or effluent from a linear alkylbenzene manufacturing process or a conventional linear detergent alcohol process, but other feeds such as jet / diesel or olefins may be used. have.

If the feed is paraffinic, the process embodiments typically and preferably further comprise dehydrogenation step (b) inserted in the sequence between adsorptive separation and alkylation and alkylation steps, wherein the modified alkylbenzene is the preferred product. In alkylation step (c). If the feed is an olefin, very obviously, dehydrogenation is not necessary. Generally, the alkylation step is followed by the sulfonation step (d), the neutralization step (e) and the formulation step (f) into the consumable cleaning article by mixing, flocculation, compression, spray-drying and the like. The optional step may comprise one or more steps and may include any step such as distillation, provided that it includes at least a certain minimum step.

In the case of producing modified alkylbenzenes, the adsorptive separation step (a) uses a hydrocarbon feed selected from olefinic feed, paraffinic feed and mixed olefinic / paraffinic feed, at an increased rate relative to the hydrocarbon feed. One or more branched hydrocarbon-rich streams comprising, for example, at least about 50% or more in relative terms and at least about 10% or more in absolute terms, i.e. One or more additional streams comprising, for example, linear acyclic aliphatic hydrocarbons in an increased proportion relative to the hydrocarbon feed (e.g., at least about 50% or greater in relative terms; For example, partial or complete separation into one or more linear hydrocarbon-rich streams. Other streams present in the process may vary in composition. Such streams include effluent streams in which undesired cyclic and / or aromatic components from the feed are generally present at levels above the feed, recycle streams and the like may also be present.

More specifically, the adsorptive separation step (a) of the process comprises first providing a hydrocarbon feed, followed by an adsorptive separation step using a porous medium (preferably), inclusions selected from urea, thiourea and alternative clathrate amides. One or more steps, including one or more steps selected from a clathrate step using a compound, and combinations thereof. This step simulates the migration of one or more layers (eg, FIG. 1 and related description of US Pat. No. 2,985,589) containing a porous medium or clathrate compound and the porous medium or clathrate compound countercurrent to the hydrocarbon stream in the layer. A simulated moving bed adsorptive separation means known in the art, including both a device, typically a highly specialized design rotary valve (see, in particular, FIG. 2 of US Pat. No. 2,985,589). US Pat. No. 2,985,589 to which reference is incorporated.

Particularly unusual and novel in the specification of the process of the present invention is that at least here, simulated moving bed adsorptive separation is used to extract essentially branched hydrocarbon-rich streams, which is why in the preparation of linear alkylbenzenesulfonate surfactants It is exactly the opposite of the implementation used. This essential difference is also related to the different content of the layers compared to conventional practice, i.e. by having a larger pore size, one or more layers containing a porous medium different from the 4 to 5Å zeolites typically used in linear alkylbenzene production Present and reorder process equipment, especially layers and equipment, so that they are connected differently to the relevant process steps. More specifically, these means allow branched streams to pass through the process, but linear hydrocarbon-rich streams useful for other purposes are present with the hydrocarbon-rich streams exited or branched from the process. Furthermore, step (a) (or step (A) when preparing a modified primary OXO alcohol) of the process of the invention is suitably at least more than the pore size required for the selective adsorption of linear acyclic hydrocarbons. Using at least one porous medium selected from the group consisting of porous media having a large minimum pore size, wherein the pore size does not exceed about 20 mm 3, and more preferably does not exceed about 10 mm 3.

If the hydrocarbon feed invariably comprises at least a level higher than at least about 10% of paraffin, eg, at least about 11 to 90% of paraffin, the process of the present invention preferably partially comprises a branched hydrocarbon-rich stream. A further step (b) of dehydrogenation as a whole. Dehydrogenation can be carried out using known catalysts and conditions.

When producing modified alkylbenzenes, regardless of the type of feed, the process of the present invention preferably comprises the preceding steps (a branched hydrocarbon-rich stream typically results in at least about 5%, more typically about olefins ultimately). The branched hydrocarbon-condensed stream prepared by one or both of an adsorptive separation step comprising optionally dehydrogenation, comprising at least 15%, generally 5 to 90% or more, is subjected to benzene, toluene and Reacting with an aromatic hydrocarbon selected from a mixture thereof (c). Preferred alkylation steps herein have a low internal isomeric selectivity of 0 to about 40 or less, preferably about 20 or less, and are more fully described and defined herein below. Such low alkylation selectivity alkylation steps are naturally considered novel in the field of modified alkylbenzene production.

The preferred method herein further preferably satisfies at least one, more preferably both, of the following conditions: As a first condition, the step (a) means comprises at least one device and at least two layers. Wherein at least one layer comprises a porous medium that is distinguished by an increased capacity to retain methyl-branched acyclic aliphatic hydrocarbons relative to the incorporation of another layer. For example, zeolites having a pore size greater than about 5 mm 3 and up to about 7 mm 3 are particularly preferred. As a second condition, step (c) has a lower internal isomeric selectivity, as defined further below, from 0 to about 40.

Preferred methods herein operate in a manner that is inconsistent or inconsistent with the conventional practice of acquiring alkylbenzenesulfonate surfactants that accept linear materials for further processing and discharge most of the branched material. It has also been found that to achieve this reversal, it is necessary to use an unusual interconnection line of the adsorptive separation operation as further described and described in the figures herein.

In addition, in the preferred method of the present application, the simulated moving bed adsorptive separation means in step (a) comprises two devices, not one. The number of devices taken with these arrangements is of particular importance in preparing the preferred compositions of the present invention and increases the specific type of branching in the hydrocarbon stream.

In addition, in certain preferred methods comprising two layers, each comprises a porous medium of a different member, each layer being controlled by one of the devices, each device being controlled by the porous medium in the layer. Eight or more ports (as defined in US Pat. No. 2,985,589) to achieve simulated migration. Each layer is further divided into a vertically located array of preferably eight or more sub-layers (see FIG. 1 of US Pat. No. 2,985,589). Also preferably, step (a) uses entirely porous media rather than inclusion compounds in the layer.

The method herein may comprise one or more steps following the alkylation step when producing modified alkylbenzenes. This step may comprise an additional step (d) of sulfonating the product of step (c). Sulfonation may be followed by further step (e) to neutralize the product of step (d). This step is followed by mixing the product of step (d) or (e) with one or more cleaning article auxiliaries to form the cleaning article.

The present invention also relates to modified alkylbenzenes prepared by any of the methods herein, as well as modified alkylbenzenesulfonic acids or sodium, potassium, ammonium or substituted ammonium forms prepared by any of the methods herein. And modified alkylbenzenesulfonate surfactants in the form of any known salt, and also includes consumable cleaning articles made by any of the methods herein.

In addition, when anionic surfactants are prepared from modified primary OXO alcohols as taught herein, all salt forms of the surfactants identified above are encompassed by the present invention.

Cleaning article embodiments herein are intended for use in laundry detergents, dishwashing detergents, hard surfaces, where they comprise modified alkylbenzene sulfonates and / or any modified primary OXO alcohol derived surfactants taught herein. Detergents and the like. In such embodiments, the content of the modified surfactant prepared by the method of the present invention is about 0.0001 to about 99.9%, typically about 1 to about 50%, and the composition further comprises a cosurfactant, builder, enzyme, bleach , From about 0.1 to about 99.9%, typically from about 1 to about 50%, of a cleaning article aid such as a bleach promoter, activator or catalyst and the like.

The invention also includes an alternative embodiment using a paraffinic hydrocarbon feed, which in particular is followed by two adsorptive separation steps arranged in the same manner as in step (a) described herein for producing the modified alkylbenzenes. An additional step is followed, not the benzene alkylation step (c), which produces a useful cleaning surfactant. The steps replacing the alkylation step (c) may comprise one or more steps selected from dehydrogenation, chlorination, sulfoxide, oxidation to C8-C20 alcohols and oxidation to C8-C20 carboxylic acids or salts thereof, optionally glucose One step is followed by amidation, conversion to nonsaccharide-derived amide surfactants such as monoethanolamide surfactants or any amide without glucose residues, and sulfonation as ester. Another alternative embodiment uses a hydrocarbon feed comprising at least 20% methyl-branched olefins; Again, this method comprises a specially arranged adsorptive separation step (a). Subsequent steps include any sulfonation subsequent to alkylation with benzene or toluene; One or more alkoxylation, sulfated, sulfonated or combinations thereof following alkylation with phenol; Any one or more alkoxylation, glycosylation, sulfated, phosphorylation or combinations thereof following hydroformylation with alcohol; Amination and oxidation with amine oxides following hydrobromination; And phosphonation.

The present invention also includes surfactants prepared by this method and cleaning articles made by this method. The present invention also encompasses particularly useful embodiments in which the adsorptive separation step (a) comprises at least one separation step using an organometal-grafted mordenite such as tin-grafted mordenite. The present invention also encompasses a method comprising the use of grafted mordenite for preparing the detergent and any corresponding surfactant and consumable product in the manner defined above using this particular porous medium.

The present invention includes many other important aspects and branches. In this way, the present invention,

Providing a hydrocarbon feed comprising a branched aliphatic hydrocarbon having 8 to 20 carbon atoms, more particularly a paraffinic hydrocarbon,

These hydrocarbon feeds may be partially or wholly prepared using porous media.

At least one branched hydrocarbon-rich stream comprising increased proportions of branched acyclic hydrocarbons relative to the hydrocarbon feed, and optionally at least one

A linear hydrocarbon-rich stream comprising increased proportions of linear aliphatic hydrocarbons relative to the hydrocarbon feed; And

Adsorptive separation into an effluent stream comprising cyclic and / or aromatic and / or ethyl- or higher higher alkyl-branched hydrocarbons, wherein the hydrocarbon stream in the one or more beds and layers retains a porous medium (A) characterized by using a simulated moving bed adsorptive separation means comprising both devices for simulating the movement of a countercurrent porous medium,

Subsequently, it may include any additional steps (B), (C) and (D) (which may include one or more steps) as follows:

Partially or wholly dehydrogenated the branched hydrocarbon-rich stream of step (A), such that an olefinic branched hydrocarbon-rich stream comprising mono-olefins (optionally at least 80% of a high proportion of paraffin is also diolefin and / or aromatic (I) may optionally be present with impurities, and optionally

Treating the olefinic branched hydrocarbon-rich stream to reduce the content of diolefinic impurities (ii), and

Treating (B) an olefinic branched hydrocarbon-rich stream to reduce the content of aromatic impurities (B);

Optionally, the mono-olefins in the olefinic branched hydrocarbon-rich stream of step (B) are known adsorbents or porous media, provided that the adsorbent or porous medium is different from the porous medium of step (A) and the olefin / paraffin separation ( Suitable, for example, for copper-treated or silver-treated zeolites X or Y), partially or fully concentrated by adsorptive separation means, and optionally, simultaneously dehydrogenating paraffins (B). Recirculating to (C); And

Reacting the olefinic branched hydrocarbon-rich stream produced in step (B) or optionally further concentrated in step (C) with carbon monoxide and hydrogen in the presence of an OXO catalyst to form a modified primary OXO alcohol. (D).

In the description of the process herein, the term "stage" means a collectively integratable group of one or more process steps. For example, step (A) is an adsorptive separation step, essentially a modified MOLEX ^R step that can be approved from UOP, which is typically arranged to enhance (reduce rather than standard practice) the branched content of hydrocarbons. . This may optionally include distillation, addition or removal steps known in the art using lower boiling hydrocarbons to wash the adsorbent as part of the same step. Step (B) is at least a dehydrogenation step, but often a dehydrogenation step including any other step as specifically mentioned above. The essential process description for step (B) can be approved by UOP Corporation, for example, as a PACOL ^R process. Step (C) is essentially a conventional OLEX ^R step available from UOP Corporation. Step (D) is preferably a step of the well known type which is referred to in the art as “one step low pressure OXO”. In relation to other steps of the process, step (D) may be supplemented by any other step, for example by catalyst removal. Unless stated otherwise, herein we will use capital letters (A, B, C ...) when referring to the steps of the process embodiments of the present invention that include preparing modified primary OXO alcohols.

These novel modified primary OXO alcohols and surfactants derivable from the above-mentioned alkylbenzenes are more soluble at the provided chain length / carbon number and, when incorporated into detergent particles, which are important in view of the increasing popularity of low washing temperatures. And unexpectedly high dissolution rates. As such, OXO alcohol and alkylbenzenes themselves have excellent utility for manufacturers of cleaning compositions such as heavy laundry detergents, dishwashing liquids and the like. All parts, ratios, and ratios herein are by weight unless otherwise indicated. All temperatures are in degrees Celsius unless otherwise specified. Relevant parts of all cited documents are incorporated herein by reference.

1-18 are schematic diagrams of certain processes according to the present invention. FIG. 8 shows the arrangement of the two adsorptive separation devices in more detail, each of the type as shown in the first two adsorptive separation steps of FIGS. 1 and 2 separately. Note that the interconnect lines of FIG. 8 are as shown in FIG. 1, but are different from those shown in FIG. 2.

Solid lines are used for essential process steps and process streams. The dashed lines represent the steps and streams that are not essential to the process, as most broadly defined, but may be present in various preferred process embodiments. Rounded rectangles represent process steps or devices. Numbered lines represent feedstocks, intermediate process streams, and products. "SOR" represents the adsorptive separation step. "4/5" indicates that microporous zeolites, in particular Ca zeolite 5kV, are used in the preparation of linear alkylbenzenes for adsorptive separation. "5/7" refers to a porous material such as ASPO-11, or monomethyl branched paraffins and / or monomethyl branched monoolefins and / or nongeminal dimethyl paraffins and / or dimethyl olefins not on the same carbon phase. It has the ability to adsorb a dimethyl hydrocarbon, aromatic or aliphatic, having the ability to adsorb, to use cyclic (5- or 6-membered or more ring) hydrocarbons or any equivalent porous material which gives off highly branched hydrocarbons. As used herein, the term "dimethyl carbon on the same carbon" As in this means that two methyl is bonded to the internal carbon atom of one of the hydrocarbons. The large-porous porous material herein should not adsorb such hydrocarbons. In contrast, the next hydrocarbon must be adsorbed. They illustrate what is represented by the term "dimethyl not on carbon" hydrocarbon:

Note that methyl residues at the backbone end are not included in the definition of the term "dimethyl, but not on the same carbon" as used herein. In addition, in line with this promise, the next hydrocarbon must be adsorbed by the large-porous porous material. It is a "monomethyl" hydrocarbon:

Large-porous porous materials suitable for use herein are described more fully in the specification below. "DEH" refers to the step of partially or totally dehydrogenating the stream (partial dehydrogenation is typical in conventional linear alkylbenzene preparations, but overall dehydrogenation can also be used herein), and "ALK" refers to the alkylation step. . Any step or device, represented by a rounded rectangle, may in fact comprise only the necessary steps or, more typically, additional steps or steps that may only be necessary in certain or preferred embodiments of the invention as most broadly defined. Include. Additional steps not shown include, for example, distillation steps of the type commonly practiced in the art.

In Figures 9-18, "DIST" represents a distillation step and "SOR O / P" represents an adsorptive olefin / paraffin separation step, e.g., step (C) in the modified primary OXO alcohol preparation described in detail below. Represents an OLEX ^R process of UOP as used in the present case, and “OXO” when present indicates a hydroformylation process step. Such process steps are well known in the art (see "Background").

With the above mentioned promise in mind, FIG. 1 shows two successive adsorptive separations followed by an adsorptive separation step (a) of the present invention as defined hereinafter, followed by a dehydrogenation step [post step (b)], And then optionally an alkylation step (following step (c)). Step (c) is optional in the present invention as most broadly defined, but is present in all preferred embodiments related to the preparation of the modified alkylbenzenes according to the present invention, when preparing modified alkylbenzenesulfonate surfactants, Typically followed by sulfonation step (d), neutralization step (e) and mixing (f) to formulate into a consumable cleaning article. Steps (d) to (f) use conventional means and are therefore not explicitly shown in FIGS.

In the process of FIG. 1, the hydrocarbon feed 1 is passed to a first adsorptive separation stage using a bed of 4-5 mm zeolite, for example, consistent with the steps of US Pat. No. 2,985,589. The linear hydrocarbon stream is discarded as effluent stream 6. For comparison, in conventional linear alkylbenzene preparations, stream 6 containing a high proportion of linear hydrocarbons is delivered to DEH, while step SOR 5/7 and related streams may not be present. In this process according to FIG. 1, the intermediate branched hydrocarbon-rich stream is retained in (2) and passed to the second adsorptive separation. The second adsorptive separation employs a particular type of porous medium, and the outlet stream (as well as the branched hydrocarbon-concentrated stream 3 (the product of step (a) as defined below)) that is delivered to the dehydrogenation reactor (DEH). Create 7). Particular types of porous media are preferably "large-pore" zeolites, such zeolites of this disclosure have a larger pore size, very preferably greater than about 5 GPa to about 7 GPa, than the zeolites used in the preparation of linear alkylbenzenes. However, larger pore materials can be used, and their pore sizes can be “tuned down” by using, for example, tin alkyl. Stream 4 represents a hydrocarbon having a high degree of dehydrogenation, and stream 8 represents a branched paraffin to be recycled. In addition, the alkylation step according to the present invention is shown to be included in a preferred embodiment of the present invention. Effluent from the alkylation step is modified alkylbenzene as defined herein.

2 is a schematic diagram illustrating the steps of another aspect of the method of the present invention. Overall, the process is similar to that of FIG. 1, but the process of FIG. 2 has a significant difference in that the pore size of the adsorbent layer is reversed, particularly in the adsorptive separation step.

4 is a schematic representation of an embodiment of the present invention starting with a hydrocarbon feedstock 23, such as a branched effluent from a conventional linear alkylbenzene process or from a conventional linear detergent alcohol process. An adsorptive separation step using a specific porous medium is used to produce the outlet stream 27 and the branched hydrocarbon-rich stream 24. The branched hydrocarbon-rich stream is dehydrogenated at the stage designated DEH. Particular types of porous media are zeolites which preferably have a larger pore size, very preferably greater than about 5 GPa to about 7 GPa, than the zeolites used in the preparation of linear alkylbenzenes. The dehydrogenated hydrocarbon stream 25 is passed to an alkylation step (ALK) from which a modified alkylbenzene product 26 is produced. Any recycle stream is shown as (28).

FIG. 3 is a schematic representation of an embodiment of the present invention similar to FIG. 4 using substantially different feedstocks and intermediate process stream compositions. For example, FIG. 3 shows, as feed 17, a C10-C14 paraffin midstream with an inherent linear / branched paraffin ratio as provided, from which cyclic, aromatic, isotopic dimethyl (gem-dimethyl), ethyl- or higher higher alkyl-branched hydrocarbons are removed as part of this process.

Comparing FIG. 3 with FIG. 4, the processes shown therein may be considered identical in that they are apparently in the same arrangement of steps. It is not so that very different results are achieved as a result of changing the hydrocarbon feed. 4 uses the effluent stream from the linear alkylbenzene production plant as the hydrocarbon feed 23 and produces significantly branched modified alkylbenzene 26. The process of FIG. 4 can be installed as an "add-on" in a standard linear alkylbenzene production plant. In contrast, FIG. 3 uses a mixture of linear and branched paraffins, a kind inherently present in jet / diesel distillates, derived from unprocessed kerosene in a linear alkylbenzene production plant as a hydrocarbon feed. . 3 process produces a modified alkylbenzene containing a mixture of methyl-branched (unconventional according to the invention) and linear (conventional) alkylbenzenes. The process of Figure 3 can be laid out as "stand-alone" which does not require connection to a conventional linear alkylbenzene production plant. Such considerations are intended to more fully explain the present invention and should not be considered as limiting.

5, 6 and 7 are schematic diagrams showing further aspects of the present invention for providing yet another different hydrocarbon feed. More specifically, these figures show a process for providing a mixed paraffin / olefin feed.

FIG. 8 illustrates in more detail the adsorptive separation processes of a particular arrangement shown in other process diagrams (eg, FIGS. 1 and 6). Each block represents an adsorptive separation device. Within each block, the vertical array of adsorptive separation layers (AC on the left in each block) is controlled by a rotary valve RV. Adsorptive separation is carried out by distillation in columns RC and EC. The streams labeled "feed", "extract" and "raffinate" of the leftmost adsorptive separation correspond to the streams labeled "1", "6" and "2" in FIG. The raffinate stream of the first adsorptive separation (and no extract as is the case in conventional linear alkylbenzene preparations) is the feed for the second adsorptive separation. The raffinate of the second adsorptive separation in FIG. 8 corresponds to stream 7 in FIG. 1. The extract of the second adsorptive separation in FIG. 8 corresponds to stream 3 in FIG. 1, which is a dehydrogenated and / or alkylated stream in this process.

As mentioned above, FIG. 8 is also provided herein to illustrate the individual adsorptive separation in more detail. Thus, while there is no connection line as shown in FIGS. 2, 3, 4, 5 and 7, any single adsorptive separation of FIGS. Can be used in more detail.

1 to 7 indicate that hydrocarbon distillate adsorbed by the porous medium is present above the adsorptive separation process labeled "SOR", while unadsorbed distillate is present as below the adsorptive separation process labeled "SOR". Promise to be. Distillates present "above" are sometimes referred to in the art as "adsorbates" or "extracts," and distillates present "below" are sometimes referred to as "rapinates" or "effluents." The "up" and "down" promised herein are intended to make the process drawings easier to read and should not be construed as limiting the actual implementation of the invention to specific geometries.

Using a principle similar to that used in FIGS. 1 to 8, FIG. 9 shows a process for preparing a modified primary OXO alcohol using a medium chain methyl-branched internal olefin having suitable carbon number for detergents as intermediate (here, OXO catalyst Mostly pre-isomerizes the internal olefins into alpha-olefins and then hydroformylates primarily at the terminal carbon atoms). More specifically, crude hydrocarbon feed 51 is distilled using distillation column DIST to ensure a hydrocarbon feed suitable for the remainder of the process. Feed 1 may preferably be a narrow-carbon range paraffin distillate. Light distillate 52 and heavy distillate 53 are also obtained, but are not further used in the preparation of the OXO alcohols of the present invention. The hydrocarbon feed 1 is delivered to a simulated moving bed adsorptive separation system comprising the devices SOR 4/5 connected in the sequence shown, followed by SOR 5/7 (each suitable MOLEX ^R type). The linear paraffin is arranged such that the concentrated linear hydrocarbon-concentrated and the stream (adsorbate) indicated by (6) in FIG. 9 exits the device SOR 4/5. The intermediate branched hydrocarbon-rich stream (rapinate) 2 enriched in methyl-branched paraffins is subjected to apparatus SOR 5/7. Discard the outlet stream 7 from SOR 5/7 containing unwanted cyclic, aromatic, ethyl- or higher higher alkyl-branched paraffins. The branched hydrocarbon-rich stream (3) from SOR 5/7, now a purified methyl-branched paraffinic stream, proceeds to, for example, a dehydrogenizer DEH of the PACOL ^R type, of which less than 20% of the predominance Is converted to the corresponding mono-olefin. Arranged simulated transfer using a similar method to separate OLEX ^R or olefins from paraffins, branching hydrocarbon-rich streams (olefin-based) 4 containing mono-olefins with unreacted paraffins and certain diolefin impurities. Proceed to SOR O / P, a bed adsorptive separation system. Suitably, the adsorbent is, for example, copper or silver on zeolite X or Y. From SOR O / P, the purified olefinic branched hydrocarbon-rich stream (adsorbate) 55, now nearly methyl-branched olefin, is run into the OXO reactor. Recycle stream 8 is mainly methyl-branched paraffin. The OXO reactor is arranged in the art as referred to in the art as a " one-step low pressure OXO process " using bulky phosphine ligands (see references in the background section). The product stream 58, which is crude reformed primary OXO alcohol, is separated from the recycleable material using distillation and other auxiliary means not shown, and the stream is a clean modified primary OXO alcohol that does not currently contain recycleable material. It is shown as (57). See the table below for a more detailed description of the composition of each stream.

FIG. 10 is similar to FIG. 9 except that after the dehydrogenation step, one or more treatment steps are incorporated to hydrogenate the diolefin impurities produced in the dehydrogenator and convert them back to mono-olefins. This is typically the DEFINE ^R type stage (UOP Corp.). In addition, there may be one or more additional aromatic hydrocarbon removal steps, such as a PEP ^R (UOP) process, which may primarily remove aromatic impurities formed during dehydrogenation.

FIG. 11 is similar to FIG. 10 except that the olefin / paraffin mixture is used as material to feed the OXO reactor and the recycle stream 8 is simplified in that it is a large fraction (> 70%) in the OXO reactor product. .

FIG. 12 is similar to FIG. 10 except that devices SOR 4/5 and SOR 5/7 are reversed.

FIG. 13 is similar to FIG. 11 except that the devices SOR 4/5 and SOR 5/7 are reversed.

FIG. 14 is similar to FIG. 12 except that SOR 4/5 is removed such that a mixture of linear and methyl-branched compounds is delivered throughout the process. The final product is mixed linear and methyl-branched primary OXO alcohols.

FIG. 15 is similar to FIG. 13 except that SOR 4/5 is removed such that linear and methyl-branched compounds are delivered throughout the process. The final product is mixed linear and methyl-branched primary OXO alcohols.

FIG. 16 is similar to FIG. 10 except that equipment is equipped to produce modified alkylbenzenes and / or modified primary OXO alcohols using olefinic branched hydrocarbon-rich streams 55.

FIG. 17 is similar to FIG. 11 except that equipment is equipped to produce modified alkylbenzenes and / or modified primary OXO alcohols using methyl-branched olefin stream 54.

FIG. 18 is equipped with equipment to produce products comprising modified alkylbenzenes and / or modified primary OXO alcohols with corresponding linear counterparts using methyl-branched olefins and linear olefin streams 61. It is similar to FIG. 14 except that.

In one aspect, the present invention relates to a process for preparing modified alkylbenzenesulfonate surfactants from hydrocarbon feedstocks. The synonyms "feed" and / or "feedstock" are used herein to refer to any hydrocarbon useful as a starting material in the process of the invention. In contrast, the term “stream” is typically used to denote a hydrocarbon that passes through one or more process steps. The hydrocarbon feed herein generally contains acyclic aliphatic hydrocarbons in useful proportions, whether olefinic or paraffinic, or may comprise a mixture of such olefins and paraffins. The raw feedstock typically further comprises varying amounts of cyclic and / or aromatic impurities, as found in kerosene, jet / diesel (middle distillate) hydrocarbon distillates. In feedstocks, olefins and paraffins generally comprise both branched and linear forms. Also, in general, branched forms in the feedstock may be undesirable or desirable for the purposes of the present invention. It is an object of the present invention to provide a cleaning article, for example, in which the high polymethyl branched hydrocarbon degree is significantly different from the gasoline preparation in which it is desirable to increase the octane rating. The present invention relates to a process for isolating particularly desired forms of hydrocarbon feeds for cleaning articles and to cleaning them with surfactants (particularly surfactants based on certain modified alkylbenzene sulfonates and / or modified primary OXO alcohols). Provided are methods for incorporation into surfactant intermediates useful in articles and such products.

The term "modified" as applied in connection with any product of the process of the present invention means that the product contains a very particular type of branch, which is surprisingly presently preferred as currently taught and used in cleaning article surfactants. It is different from the linear structure. The term “modified” also refers to conventional highly-branched cleansing surfactant structures such as those found in tetrapropylene benzene sulfonate, and “two-tailed” or “Guerbet” or All other conventional branched structures, such as aldol-derived branched structures, are used to distinguish them from the products herein.

Hydrocarbon feeds herein may generally vary very broadly, but typically include methyl-branches such as monomethyl, dimethyl (including isotopical dimethyl), trimethyl, polymethyl, ethyl and higher higher alkyl branches. do. The hydrocarbon feed may contain quaternary carbon atoms. However, resistance to quaternary carbon atoms in the feed is much better than when the process of the present invention comprises an alkylation step as taught below. In embodiments of the present invention that include an OXO process step but no alkylation step, the preferred feed herein does not necessarily contain quaternary carbon atoms. Preferred components for the purposes of the present invention include some proportion of monomethyl-branched, dimethyl-branched, not tri-branched, and especially trimethyl-branched, carbon content above about 14 do. Hydrocarbon feeds generally contain a useful ratio, such as, for example, a cleaning agent surfactant of the desired type, or a non-cyclic hydrocarbon having from about 9 to about 20 carbon atoms, depending on the cleaning product use of the modified surfactant produced. For example, 5 to 40% or more. More preferably, when producing modified alkylbenzenes and alkylbenzenesulfonates, the carbon number of the acyclic aliphatic hydrocarbons in the feedstock is about 10 to about 16, more preferably about 11 to about 14.

The process of the present invention includes a specially defined adsorptive separation step, in which an alkylation step is also necessary to prepare modified alkylbenzenes and alkylbenzenesulfonates. If the feedstock is paraffinic, the process embodiments are usually and preferably referred to as SOR 4/5 or SOR 5/7 in the figures between the adsorptive separation step and the alkylation step or when producing modified primary OXO alcohols. And a dehydrogenation step inserted in the sequence between the type adsorption step and the OXO process step. In general, an alkylation step or an OXO step may be followed by additional steps such as subsequent sulfonation followed by a neutralization step and formulation into a consumable cleaning article by mixing, flocculation, compression, spray-drying, and the like. Also, in general, any step may include one or more steps if the step includes at least one step.

The adsorptive separation step (a) is characterized in that a hydrocarbon feed selected from an olefin feed, a paraffin feed and a mixed olefin / paraffin feed is prepared by branching acyclic hydrocarbons (especially Type, in particular methyl-branched paraffin or methyl-branched mono-olefin, in an increased proportion (eg, at least about 50% or more, more preferably at least about 100% or more, typically 3 At least one branched hydrocarbon-enriched stream comprising at least about 10%, at least about 10%, typically at least 20%, more preferably at least 30 to about 90%, by weight; And optionally, an increased proportion (eg, at least about 50% or greater, more preferably at least about 100% or greater, typically 3 or 4 times, in linear terms relative to the hydrocarbon feed) At least about 10 wt%, typically at least 20 wt%, more preferably at least 30 to about 90 wt%) in absolute terms; And partially or wholly separation into one or more of the effluent streams comprising other impurities such as cyclic and / or aromatic hydrocarbons or isotopical dimethyl hydrocarbons, ethyl-branched hydrocarbons or highly-branched hydrocarbons.

Other streams present at any stage in the process of the invention may vary in composition. Such a stream may comprise an outlet stream in which undesired cyclic and / or aromatic components from the feed are generally present at levels above the feed component; Recycle streams and the like having compositions that depend on the part of the process they are connected to. Known processes, such as in US Pat. No. 5,012,021 or US Pat. No. 4,520,214, both of which are incorporated herein by reference, can be used herein to convert impurities such as certain diolefins back to monoolefins using selective catalysts. have. Other processes that may optionally be incorporated herein to selectively remove aromatic byproducts formed in paraffin dehydrogenation include aromatics that may include one or more aromatic hydrocarbon removal regions and / or, for example, sulfolane and / or ethylenediamine. Processes of US Pat. No. 5,300,175 and US Pat. No. 5,276,231, including the use of extraction solvents for hydrocarbons.

More specifically, the adsorptive separation step or portion of the process used to increase the content of branched hydrocarbons in the feed comprises at least one step selected from providing a suitable hydrocarbon feed and an adsorption step using a porous medium, One or more steps comprising one or more steps selected from inclusions using a inclusion compound selected from urea, thiourea and replacement clathrate amides and combinations thereof. Very preferably, when used in combination, the at least one step is an adsorptive separation step using a larger-pore type porous medium, which is more fully described below. Step (a) (or step (A) when preparing a modified primary OXO alcohol) is one that contains a porous medium or clathrate compound (see, eg, FIG. 1 and related description of US Pat. No. 2,985,589). Apparatus for simulating the migration of porous layers or clathrate compounds countercurrent to hydrocarbon streams in the above layers and in these layers (see, in particular, FIG. 2 and related descriptions of US Pat. No. 2,985,589, or in the preparation of linear alkylbenzenesulfonates) Deformers) simulated moving bed adsorptive separation means well known in the art, including both, US Pat. No. 2,985,589, which is incorporated herein in its entirety. The device is typically a rotary valve of a very specialized design. In general, valves of the same type as used in current linear alkylbenzene preparations can be used herein. Adsorptive separation conditions, such as pressure, temperature and time, may be as used in the art (see US Pat. No. 2,985,589).

Particularly unusual and novel in the specification of the process of the invention is that at least here, simulated mobile bed adsorptive separation is used to extract the required branched hydrocarbon-rich stream, which is used in the preparation of linear alkylbenzenesulfonate surfactants. It is exactly the opposite of enforcement. This essential difference also alters the incorporation of the layers to contain different porous media than the 4-5 Å zeolites generally used in linear alkylbenzene preparation, and rearranges the process equipment, especially the layers and apparatus, to which processes are involved. This involves connecting differently from the steps. More specifically, these means arrange for the branched stream to be delivered throughout the process but any linear hydrocarbon-rich stream useful for other purposes is present with or with the branched hydrocarbon-rich stream from the process.

If the hydrocarbon feed comprises less than about 5% of the olefins, the process of the present invention preferably comprises a further step (b) of partially or totally dehydrogenating the product of step (a), or to produce a modified primary OXO alcohol. In the case (B). Dehydrogenation can be carried out using any known dehydrogenation catalyst, such as the De-H family (UOP), which is further described below. Dehydrogenation conditions are similar to those used in current linear alkylbenzenesulfonate preparations.

When producing modified alkylbenzenes, regardless of the type of feedstock to be treated, the process of the invention preferably comprises the product of step (a), or if step (b) is also present as a preceding step, (C) reacting the product of step (b) subsequent to step (a) with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst. Preferred alkylation steps herein have a low internal isomeric selectivity of from 0 to about 40, preferably up to about 20, more preferably up to about 10, as described more fully and defined herein below. This low internal isomeric selectivity is of course considered novel.

In one method, the alkylation step is performed herein in the presence of excess paraffin, which is recovered and recycled to the dehydrogenator. In another method, the alkylation step is carried out in the presence of a 5-10 fold excess of arene. These methods can be combined arbitrarily.

If the final branched hydrocarbon-rich stream, i.e., the product of step (a) contains a significant amount of olefins, for example at least about 5% in total, these streams can be passed directly to alkylation step (c) and then recovered The paraffins can be recycled to a dehydrogenation reactor for partial or total conversion to olefins (see, eg, FIGS. 5, 6 and 7).

Very important for the present invention, the preferred method herein further preferably satisfies one or more, more preferably both of the following conditions: As a first condition, the means (or modified) of step (a) In the case of preparing a primary OXO alcohol, the step (A) means comprises at least two devices (e.g., the aforementioned rotary valve or any equivalent means) and at least two layers, one of which The above includes a porous medium which is distinguished by an increased capacity to retain methyl-branched acyclic aliphatic hydrocarbons relative to the incorporation of another layer. For example, zeolites having a pore size that is at least about 20 mm 3 or less, more preferably about 10 mm 3 or less, even more preferably about 7 mm 3 or less, at least exceeding the size used in conventional linear alkylbenzene preparations, or certain silicoalumino Other porous media, such as phosphate or Mobil MCM type materials, are suitable herein when the pore size is as described. When using porous materials having a pore size of about 7 mm or larger, it is often very desirable to "miniaturize" the pore openings, for example by grafting tin alkyl in the pore openings (see, for example, the entirety of which is incorporated herein by reference). EP 559,510 A). As a second condition, in the case of producing modified alkylbenzenes, step (c) has a lower internal isomer selectivity of 0 to about 40 or less, preferably as further defined below.

In another preferred method, the at least one layer comprises a porous medium conventional in the preparation of linear alkylbenzenes; Step (c) of the process wherein the bed increases, in part or in whole, the proportion of methyl-branched acyclic aliphatic hydrocarbons in the stream delivered to step (c) of the process, and is partially or wholly removed as an effluent in step (a). In a manner consistent with the partial or total reduction in the proportion of linear acyclic aliphatic hydrocarbons delivered. That is, the preferred method herein is manipulated in a way that is inconsistent and inconsistent with conventional practice for preparing alkylbenzenesulfonate surfactants, which discharges branched material and accommodates linear material for further processing. It has also been found that in order to achieve this inversion, it is necessary to use an unusual interconnection of the adsorptive separation operation as already briefly described and further described in the figures herein.

Also very importantly, in the preferred method herein, the simulated moving bed adsorptive separation means in step (a) (or step (A) when producing a modified primary OXO alcohol) is porous in at least two independent layers. It includes two devices or a single device that can simulate the movement of the medium. That is, for example, a device as taught in US Pat. No. 2,985,589 will not be satisfactory in all of the preferred methods herein using a single device. The number of devices selected together with the arrangement of the devices is particularly important for preparing the preferred compositions of the present invention. Thus, a hypothesis not known from the art, increasing linear hydrocarbon purification can be performed by two devices and two layers connected in series. The highly linear adsorbate of the first stage is passed to the second stage adsorptive process inlet for further purification. This arrangement is excluded from the present invention because the steps are inadequately linked, thereby increasing the linearity and purity of the hydrocarbon. As already described, the method of the present invention passes the branched stream through various steps that require the connection of the device in accordance with the purpose. This increases certain types of branches in the hydrocarbon streams herein.

Further very importantly in the preferred method herein, there are two layers, each comprising a different medium of porous media, each layer controlled by one device, each device being controlled by one of the porous media in that layer. It includes eight or more ports to achieve simulated movement. Each layer is more preferably divided into a vertically located array of eight or more sub-layers. Also preferably, step (a) uses exclusively porous media in the layer. Thus, the present invention may employ conventional layers and devices of the general type described in US Pat. No. 2,985,589, although their number and connection to the method of the present invention are novel and precedent in alkylbenzenesulfonate production plants. It was not there.

In addition, in order to more fully describe what has already been described, in certain embodiments of the preferred process herein, the linear hydrocarbon-rich stream is present in step (a), wherein step (a) is used to linearize the hydrocarbon feed. Adsorbing the hydrocarbon-rich stream and the intermediate branched hydrocarbon-rich stream and draining the linear hydrocarbon-rich stream for the essential purpose of the process by one simulated moving bed and then (a-ii) the intermediate branch. The concentrated hydrocarbon-rich stream compared to the branched hydrocarbon-rich stream and the branched hydrocarbon-rich stream comprising an increased proportion of branched (more particularly methyl-branched) acyclic aliphatic hydrocarbons relative to the linear hydrocarbon-rich stream. A discharge stream comprising at least an increased proportion of cyclic and / or aromatic hydrocarbons is subjected to adsorptive separation by another simulated moving bed. And a step.

The discharge stream in steps (a-ii) may further comprise undesired branched hydrocarbons selected from isotopically branched dimethyl branched hydrocarbons, ethyl branched hydrocarbons and hydrocarbons branched with higher alkyl than ethyl; Here, the acyclic aliphatic hydrocarbons of the intermediate branched hydrocarbon-rich stream and the branched hydrocarbon-rich stream are higher than the reduced proportions of the same elemental dimethyl branched hydrocarbons, ethyl branched hydrocarbons and ethyl branched hydrocarbons compared to the hydrocarbon feed. Branched hydrocarbons. In general, the minimum "increase rate", "decrease rate" or "high" of any component at any step herein corresponds to an increase (increase) or decrease in a rate useful for the purposes of the present invention described in practice. do. Such amounts are fully described throughout the specification.

Also in this method, the stream composition is at least greater than about the maximum pore size of the zeolite of step (ai) and the member selected from the group consisting of 4-5 mm pore size zeolites in step (ai). Can be achieved by selecting as a porous medium a member selected from the group consisting of a porous medium having a pore size of about 10 mm 3 or less.

In another preferred embodiment, step (a) comprises (ai) a hydrocarbon feed comprising an acyclic aliphatic hydrocarbon-rich stream comprising linear- and branched (eg preferred types described above) acyclic aliphatic hydrocarbons. And adsorbing to a first effluent stream comprising at least an increased proportion of cyclic and / or aromatic hydrocarbons relative to the hydrocarbon feed, and then (a-ii) the acyclic aliphatic hydrocarbon-concentrated stream to the branched hydrocarbon- Adsorptive separation into a concentrated stream and a linear hydrocarbon-condensed stream, wherein the adsorptive separation is carried out using simulated moving bed adsorptive separation means. Unless stated otherwise herein, "branched hydrocarbon-rich stream" is the final stream of step (a), and further modifiers such as "middle" may be used to adsorb the process of the invention, even if the branched hydrocarbon is concentrated. It is prefixed with a name to indicate that the stream needs to be processed further before being passed to another step in the separation phase. In addition, as described above, the adsorptive separation step (a) may freely include any other conventional step, such as distillation, when the adsorptive separation is performed. Thus, currently commercial MOLEX ^R plants typically further comprise distillation at this stage and may be useful herein.

In addition, the present invention further comprises that the first outlet stream in step (ai) further comprises an undesired branched hydrocarbon selected from isotopically branched dimethyl branched hydrocarbons, ethyl branched hydrocarbons and hydrocarbons branched with higher alkyl than ethyl. Where the acyclic aliphatic hydrocarbon-rich stream and the branched hydrocarbon-rich stream each contain reduced proportions of the same elemental dimethyl branched hydrocarbons, ethyl branched hydrocarbons and hydrocarbons branched with higher alkyl than ethyl relative to the hydrocarbon feed. Include. In such an embodiment, the stream composition is a porous medium, at least greater than the approximately maximum pore size of the zeolite of step (a-ii) and the member selected from the group consisting of zeolites of 4-5 mm pore size in step (ai). It can be accomplished by selecting a member selected from the group consisting of porous media having a pore size of about 10 mm 3 or less in (ai).

More generally, the invention relates to a process wherein step (a) is selected from the group consisting of porous media in which the minimum pore size is larger than the pore size required for the selective adsorption of linear acyclic hydrocarbons and the pore size does not exceed about 20 mm 3. It relates to a method comprising using the above porous medium.

As noted above, preferred methods herein include mordenite wherein the alkylation step (c) has an internal isomeric selectivity of 0 to 20, and the preferred alkylation step (c) is partially or wholly acidic, consistent with the internal isomeric selectivity. And a method of using an alkylation catalyst selected from the group consisting of zeolite beta which is partially or wholly acidic. Preferred alkylation catalysts include H-mordenite and H-beta, more preferably partially or wholly dealuminated H-mordenite.

With regard to the preparation of modified alkylbenzenes and modified alkylbenzenesulfonates, the invention also preferably relates to a process wherein the hydrocarbon feed comprises at least about 10% of methyl-branched paraffins having a molecular weight of about 128 to about 282. Wherein the method comprises a dehydrogenation step (b). More preferably in this embodiment, the hydrocarbon feed comprises at least about 20% methyl-branched paraffins having a molecular weight of about 128 to about 226, the process comprising dehydrogenation step (b) and alkylation step (c) And wherein the hydrocarbon feed comprises at least about 10% methyl-branched olefins having a molecular weight of about 126 to about 280. More preferably, in this embodiment, the hydrocarbon feed comprises about 50% methyl-branched olefins having a molecular weight of about 126 to about 224, and the process does not comprise a dehydrogenation step (b).

In the case of a corresponding process for producing modified primary OXO alcohols, the above ranges may be somewhat expanded to match those affecting the total carbon number of at least about C20. More preferably, the upper limit of paraffin molecular weight 226 can be expanded to about 254, and the upper limit of olefin molecular weight 224 can be extended to about 252.

Among the utilities useful to detergent manufacturers, the hydrocarbon feed or feedstock herein may be adsorptive raffinate or effluent from a linear alkylbenzene process or from a conventional linear detergent alcohol process.

The method herein may comprise one or more steps following the alkylation step. Such steps may comprise an additional step (d) of sulfonating the product of step (c). Sulfonation may be followed by further step (e) to neutralize the product of step (d). These steps may be followed by step (f) of mixing the product of step (d) or (e) with one or more cleaning article aids to form a cleaning article.

Thus, the process herein comprises the steps of (d) sulfonating the modified alkylbenzene product of step (c), neutralizing the modified alkylbenzenesulfonic acid product of step (d), and step (d): Or (e) all further steps of (f) mixing the modified alkylbenzenesulfonic acid or modified alkylbenzenesulfonate surfactant product with at least one cleaning article aid to form a cleaning article. Include. In one such embodiment, prior to the sulfonation step, the modified alkylbenzene, the product of step (c), is blended with the linear alkylbenzene prepared by conventional methods. In another such embodiment, in any step subsequent to the sulfonation step, the modified alkylbenzene sulfonate, the product of step (d), is blended with the linear alkylbenzene sulfonate prepared by conventional methods. In this blending embodiment, the ratio of modified alkylbenzene to linear alkylbenzene in the preferred process is about 1: 100 to about 100: 1. If a relatively more linear product is desired, the preferred ratio is about 10:90 to about 50:50. If a relatively more branched product is desired, the preferred ratio is from about 90:10 to about 51:49.

In addition, the present invention provides modified alkylbenzenes prepared by any of the methods herein, as well as modified alkylbenzenesulfonic acids, or any known salt form, such as sodium form, potassium form, ammonium form, or substituted ammonium form. Alkylbenzenesulfonate surfactants modified with isotropic, and consumable cleaning articles made by any of the methods herein.

Cleaning article embodiments herein include laundry detergents, dishwashing detergents, hard surface detergents, and the like. In such embodiments, the content of the modified alkylbenzenesulfonate prepared by the present invention or the surfactant derived from the modified primary OXO alcohol and the like is about 0.0001 to about 99.9%, typically 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 a cleaning aid aid, such as a cosurfactant, builder, enzyme, bleach, bleach promoter, activator or catalyst, and the like.

Preferred consumable cleaning articles produced by this method suitably comprise from about 1 to about 50% modified alkylbenzenesulfonic acid and include enzymes, non-phosphate builders, polymers, activated bleaches, catalyzed bleaches, photobleaches and About 0.0001 to about 99% of a cleaning article aid selected from the mixture thereof.

Alternative Method Aspects

The present invention encompasses an alternative embodiment, followed by two specially arranged adsorptive separations followed by additional steps leading to a useful cleaning surfactant. Thus, (I) the branched hydrocarbon-rich stream comprises at least about 10% paraffins with methyl side chains, the methyl side chains are distributed in paraffins such that the paraffin molecules have from 0 to about 3 or less methyl side chains, At least about 90% of the branches are located in paraffin to occupy a position other than to form the same elemental dimethyl and / or quaternary residues, and the separation is performed by two or more porous media having different pore sizes from the simulated mobile bed adsorptive separation means. More preferably at least about 85% of a saturated acyclic aliphatic hydrocarbon having a carbon content of C8-C20, characterized in that the hydrocarbon feedstock is carried out by means comprising at least two adsorptive separation steps. Separating into a branched hydrocarbon-rich stream consisting essentially of these; And (II) at least one step selected from dehydrogenation, chlorination, sulfoxide, oxidation to C8-C20 alcohols, and oxidation to C8-C20 carboxylic acids or salts thereof, enriched in branched hydrocarbons. Subsequently, the method comprises the step of converting to a surfactant, optionally by one of the steps of glucose amidation, conversion to nonsaccharide-derived amide surfactant and sulfonation as ester.

In an alternative embodiment, (I) the branched hydrocarbon-rich stream comprises at least about 10% of the sum of the olefins and their saturated homologues with methyl side chains, the methyl side chains, the acyclic aliphatic hydrocarbon molecules are methyl Distributed in the mixture with 0 to about 3 or less side chains, wherein the branch is located within the acyclic aliphatic hydrocarbon molecule such that at least about 90% of the branches occupy a position other than to form the same elemental dimethyl moiety, the separation being simulated The hydrocarbon feedstock is characterized in that it is carried out by means comprising at least two adsorptive separation steps using at least two porous media having different pore sizes and moving bed adsorptive separation means, the olefin having a carbon content of C8-C20. System acyclic aliphatic hydrocarbons or mixtures thereof and mixtures thereof with saturated homologs, preferably with Consisting of olefinic branched hydrocarbon-enriched stream to the separating; And (II) optionally sulfonation of a stream enriched in olefinic branched hydrocarbons following alkylation with benzene or toluene; One or more alkoxylations, sulfates, sulfonations or combinations thereof following alkylation with phenols; Hydroformylation followed by optionally one or more alkoxylation, glycosylation, sulfated, phosphorylation or combinations thereof; Sulfonation; Epoxidation; Amination and oxidation with amine oxides following hydrobromination; And converting to the surfactant by an additional step comprising phosphonation.

In view of the alternative methods included, the present invention also includes surfactants prepared by such methods and cleaning articles made by such methods.

Aspects of the present invention will now be discussed and described in more detail.

Modified Alkylbenzene and Alkylbenzenesulfonate Products

As described above in the gist of the present invention, the present invention relates to a process for preparing modified alkylbenzenesulfonate surfactants suitable for use in cleaning articles such as laundry detergents, hard surface cleaners, dishwashing detergents and the like.

The terms "modified alkylbenzenesulfonate surfactants" and "modified alkylbenzenes" refer to products according to the process of the invention. The term "modified" as applied to novel alkylbenzenesulfonates or novel alkylbenzenes (MABs), refers to all alkylbenzenesulfonate surfactants in which the products of the present invention have been used in the industry for consumer-consumable cleaning compositions. It is a modifier indicating the difference in composition. Most particularly, the compositions of the present invention differ in composition from so-called "ABS" or poorly biodegradable alkylbenzenesulfonates and so-called "LAS" or linear alkylbenzenesulfonate surfactants. Conventional LAS surfactants are currently used commercially in several processes, including those following the alkylation of HF- or aluminum chloride-catalyzed benzenes. Other commercially available LAS surfactants include LAS prepared by the DETAL ^R process. In addition, preferred alkylbenzenesulfonate surfactants prepared using the preferred low internal isomer selectivity alkylation step, in composition, are those prepared by alkylating linear olefins using a fluorinated zeolite catalyst system that is considered to include mordenite. Different. Without being limited by theory, the modified alkylbenzenesulfonate surfactants of the present invention are specifically considered to be slightly branched. They typically contain a number of isomers and / or homologs. Often, in many of these classes (often dozens to hundreds) the total amount of 2-phenyl isomers is relatively high and the 2-phenyl isomer content is at least 25% and typically at least 50% or even 70%. In addition, the modified alkylbenzenesulfonate products of the present invention are known, for example, because they have improved surfactant efficacy and low tendency from solution to phase-separated internal isomers, especially in the presence of hard water. The physical characteristics are different from the active agent.

Feeds and Streams in the Process

The term "feed" is used herein to refer to a material that has not yet been processed by the method of the present invention. However, the term "feed" means that if an optional (eg, adsorptive separation on 5Å Ca-zeolitic phase) step is applied to such a material, such treatment is provided that the first treatment of the method of the invention It may be used only as it happens before the required steps.

The term "stream" is used herein to refer to a material that undergoes one or more steps of the process of the invention.

The term "branched hydrocarbon-rich stream", unless otherwise specified, refers to (i) relatively acyclic C8-C20 hydrocarbons branched relative to the parent distillate or feed, which is not processed in the process of the present invention. At a rate of about 10% or more, preferably about 100% or more (ie, 2 times), more preferably 3 times, 4 times or more; Or (ii) in absolute terms, when the process produces modified alkylbenzenes or modified alkylbenzenesulfonates, branched acyclic C8-C20 hydrocarbons, more preferably from about C10 to about C14 hydrocarbons It refers to any processed hydrocarbon distillate that contains at least%, preferably at least about 10%. What is referred to as a branched hydrocarbon can be any ratio of olefins, paraffins or mixed olefins / paraffins, unless otherwise specified otherwise. (Specific preferred methods include processes for preparing modified primary OXO alcohols as shown in FIG. 9 and higher starting materials from paraffinic feeds, but more generally, variations of these methods include olefins System feeds may be used). The branch is preferably a monomethyl branch or a separate (but not on the same carbon) dimethyl branch.

The term "linear hydrocarbon-rich stream" refers to any process containing, in the process of the invention, higher weight percent normal (n-) acyclic hydrocarbons than the raw distillate or feed unless otherwise specified. Refers to a treated hydrocarbon distillate.

More particularly, “linear hydrocarbon-concentrated” means (iii) at least about 10%, preferably linear acyclic C8 to about C20 hydrocarbons, relative to the parent distillate or feed that is not processed in the process of the invention. Preferably at least about 100% (ie, 2 times), more preferably 3 times, 4 times or more; Or (iv) absolutely processed hydrocarbon distillate containing at least about 5%, preferably at least about 10%, linear acyclic C8 to about C20 hydrocarbons. Linear hydrocarbons may be olefins, paraffins or mixed ratios of olefins / paraffins in any proportion, unless more specifically indicated.

Modifiers such as “middle” are used to denote a branched hydrocarbon-rich stream, which, when used with a branched hydrocarbon-rich stream, does not completely pass through the adsorptive separation step (a) of the process of the invention. Other modifiers such as "olefinic" or "paraffinic" can be used to indicate which stream predominantly contains either olefinic or paraffinic hydrocarbons.

The feeds and streams of the present invention relating to both embodiments comprising alkylation and those involving OXO reaction (or simultaneous use of both) are further described in Table 1 below. The numbers in the leftmost column refer to the feeds and streams shown in FIGS.

Stream Stream type / name Exemplary Source (for Feed) or Composition (for Stream) Predominant ingredient (s) One Hydrocarbon feed Jet / kerosene distillates, preferably from light crude oil. When producing modified OXO alcohols, the preferred feed is finite distillate (e.g., 3, 2, 1 or carbon strands, or non-infinite distillate). b-paraffins / l-paraffins 2 Branched Hydrocarbon-Concentrated Stream (Medium) Mainly branched paraffins; Still contains cyclic, aromatic hydrocarbons b-paraffin 3 Branched Hydrocarbon-Concentrated Stream Mainly methyl branched paraffin b-paraffin 4 Branched Hydrocarbon-Concentrated Stream (olefinic) Predominantly methyl branched paraffins; Methyl-branched olefins are present, for example, up to about 20%; Perhaps diolefin impurities also exist b-paraffins / b-olefins 5 Modified alkylbenzenes Predominantly methyl-branched alkylbenzenes Modified Alkyl Benzene Prepared by the FIG. 1 Process Using an Alkylation Step 6 Linear hydrocarbon-concentrated stream Mainly linear paraffin l-paraffin 7 Outlet Stream (cyclic / aromatic hydrocarbons) Paraffin branched with cyclic, aromatic, ethyl and higher alkyl 8 Recycle stream Predominantly methyl-branched paraffins b-paraffin 9 Hydrocarbon feed Jet / kerosene distillates, preferably from light crude oil b-paraffins / l-paraffins 10 Branched Hydrocarbon-Concentrated Stream (Medium) Mainly methyl branched and linear paraffin b-paraffins / l-paraffins 11 Branched Hydrocarbon-Concentrated Stream Mainly methyl branched paraffin b-paraffin 12 Branched Hydrocarbon-Concentrated Stream (olefinic) Predominantly methyl branched paraffins; Methyl-branched olefins should be present, for example, up to about 20% b-paraffins / b-olefins 13 Modified alkylbenzenes Predominantly methyl-branched alkylbenzenes Modified alkylbenzenes prepared by the FIG. 2 process using an alkylation step 14 Outlet Stream (cyclic / aromatic hydrocarbons) Cyclic, aromatic, ethyl- and higher higher alkyl-branched paraffins

Stream Stream type / name Exemplary Source (for Feed) or Composition (for Stream) Predominant ingredient (s) 15 Linear hydrocarbon-concentrated stream Mainly linear paraffin l-paraffin 16 Recycle stream Predominantly methyl-branched paraffins b-paraffin 17 Hydrocarbon feed Jet / kerosene distillates, preferably from light crude oil b-paraffins / l-paraffins 18 Branched Hydrocarbon-Concentrated Stream Mainly methyl branched and linear paraffin b-paraffins / l-paraffins 19 Branched hydrocarbon-rich stream (olefinic) Predominantly methyl-branched paraffins and linear paraffins; must contain some linear and methyl branched olefins b-paraffins / l-paraffins / b-olefins / l-olefins 20 Linear and modified alkylbenzenes Mainly methyl-branched alkylbenzenes and linear alkylbenzenes Linear and modified alkylbenzene mixtures prepared by the FIG. 3 process 21 Discharge stream Cyclic, aromatic, ethyl- and higher higher alkyl-branched paraffins 22 Recycle stream Predominantly methyl-branched paraffins and linear paraffins b-paraffin l-paraffin 23 Hydrocarbon feed Mixtures of cyclic and aromatic with branched paraffins fed from conventional LAB plant effluents, for example MOLEX ^R effluents b-paraffin 24 Branched Hydrocarbon-Concentrated Stream Predominantly methyl-branched paraffins b-paraffin 25 Branched hydrocarbon-rich stream (olefinic) Predominantly methyl-branched paraffins; Methyl-branched olefins, for example, should be present in about 20% or less b-paraffins / b-olefins 26 Modified alkylbenzenes Predominantly methyl-branched alkylbenzenes Modified Alkylbenzene Prepared by the FIG. 4 Process 27 Discharge stream Cyclic, aromatic, ethyl- and higher higher alkyl-branched paraffins 28 Recycle stream Predominantly methyl-branched paraffins b-paraffin 29 Hydrocarbon feed F. T. gasoline, highly branched distillate; digested from slack wax; Decomposition from Flexicoker or Fluidcoker b-olefin / l-olefin / b-paraffin / l-paraffin 30 Branched Hydrocarbon-Concentrated Stream (Medium) Predominantly methyl-branched olefins and linear olefins; typically containing certain linear and methyl branched paraffins b-olefin / l-olefin / b-paraffin / l-paraffin 31 Branched Hydrocarbon-Concentrated Stream Predominantly methyl branched olefins and methyl branched paraffins; Variable ratio b-olefin / b-paraffin 32 Branched hydrocarbon-rich stream (olefinic) Predominantly methyl branched paraffins; Methyl branched olefins will be present in less than about 20% b-paraffins / b-olefins 33 Modified alkylbenzenes Predominantly methyl-branched alkylbenzenes Modified Alkylbenzene Prepared by the FIG. 5 Process

Stream Stream type / name Exemplary Source (for Feed) or Composition (for Stream) Predominant ingredient (s) 34 Outlet Stream (cyclic / aromatic hydrocarbons) Cyclic, aromatic, ethyl- and higher higher alkyl-branched hydrocarbons 35 Linear hydrocarbon-rich stream (which may include cyclic / aromatic hydrocarbons) Mainly linear olefins and linear paraffins l-olefin / l-paraffin 36 Recycle stream Predominantly methyl-branched paraffins b-paraffin 37 Hydrocarbon feed F. T. gasoline, highly branched distillate; digested from slack wax; Decomposition from Flexicoker or Fluidcoker b-olefin / l-olefin / b-paraffin / l-paraffin 38 Branched Hydrocarbon-Concentrated Stream (Medium) Branched olefins, branched paraffins, cyclic and aromatic hydrocarbons b-olefin / b-paraffin 39 Branched Hydrocarbon-Concentrated Stream Predominantly methyl branched olefins and methyl branched paraffins; Variable ratio b-olefin / b-paraffin 40 Branched Hydrocarbon-Concentrated Stream (olefinic) Predominantly methyl branched paraffins; Methyl branched olefins will be present, for example, up to about 20% b-paraffins / b-olefins 41 Modified alkylbenzenes Predominantly methyl-branched alkylbenzenes Modified Alkylbenzene Prepared by the FIG. 6 Process 42 Linear hydrocarbon-concentrated stream Mainly linear olefins and linear paraffins l-olefin / l-paraffin 43 Outlet Stream (cyclic / aromatic hydrocarbons) Cyclic, aromatic, ethyl- and higher higher alkyl-branched hydrocarbons 44 Recycle stream Predominantly methyl-branched paraffins b-paraffin 45 Hydrocarbon feed F. T. gasoline, highly branched distillate; digested from slack wax; Decomposition from Flexicoker or Fluidcoker b-olefin / l-olefin / b-paraffin / l-paraffin 46 Branched Hydrocarbon-Concentrated Stream Predominantly methyl-branched olefins and linear olefins; typically containing certain linear and methyl branched paraffins b-olefin / l-olefin / b-paraffin / l-paraffin 47 Branched Hydrocarbon-Concentrated Stream (olefinic) Predominantly linear and methyl-branched paraffins; Will contain certain linear and methyl branched olefins b-paraffins / l-paraffins / b-olefins / l-olefins 48 Modified alkylbenzenes Mainly methyl-branched alkylbenzenes and linear alkylbenzenes Modified Alkylbenzene Prepared by the FIG. 7 Process 49 Exhaust Stream (Cyclic / Aromatic Hydrocarbons) Cyclic, aromatic, ethyl- and higher higher alkyl-branched hydrocarbons 50 Recycle stream Predominantly methyl-branched paraffins and linear paraffins b-paraffin l-paraffin 51 Crude hydrocarbon feed Preferably kerosene-range paraffins from light paraffinic crude oil; 360-500 ° F (182-277 ° C) b-paraffin l-paraffin

Stream Stream type / name Exemplary Source (for Feed) or Composition (for Stream) Predominant ingredient (s) 52 Light distillate (not used to produce OXO alcohol or modified LABs) Light distillate—eg from 360 ° F. to product distillate 53 Heavy distillate (not used to produce OXO alcohol or modified LABs) Heavy distillates—eg, initial product distillates to 530 ° F. 54 Branched hydrocarbon-rich stream (olefinic) (de-diolefinated) Mainly methyl-branched paraffins and methyl-branched olefins will, for example, be present in about 20% or less (essentially free of diolefins and / or aromatic hydrocarbons) b-paraffin b-olefin 55 Branched hydrocarbon-rich stream (olefinic) (de-paraffinized) Predominantly methyl-branched olefins b-olefin 56 Modified Primary OXO Alcohol Mainly Modified Primary OXO Alcohol + Trace Paraffin Modified Primary OXO Alcohol 57 Modified Primary OXO Alcohol (Recycleless) Modified Primary OXO Alcohol Modified Primary OXO Alcohol 58 Crude-modified first class OXO alcohol Mainly modified primary OXO alcohol + certain alpha-, omega-diol + trace paraffin Modified Primary OXO Alcohol 59 Modified alkylbenzene + paraffin Predominantly methyl-branched paraffins + up to about 30% modified alkylbenzenes b-paraffin-modified alkylbenzenes 60 Modified Primary OXO Alcohol + Paraffin Predominantly methyl-branched paraffin + up to about 25% modified primary OXO alcohol b-paraffin-modified primary OXO alcohol 61 Linear Olefin + Methyl-Branched Olefin in Paraffin Mainly linear paraffins and methyl-branched paraffins, linear olefins and methyl-branched olefins will be present, for example, at up to about 20% (essentially free of diolefins and / or aromatic hydrocarbons) (linear compounds are branched Effectively "dilutes" hydrocarbons) b-paraffin l-paraffin b-olefin l-olefin 62 Linear olefins and methyl-branched olefins Predominantly linear olefins and methyl-branched olefins b-olefin 63 Mixtures of Modified Primary OXO Alcohols and Regular OXO Alcohols Mainly conventional OXO alcohols and modified primary OXO alcohols + trace paraffins Modified Primary OXO Alcohol Linear OXO Alcohol 64 Another mixture of modified primary OXO alcohols and conventional OXO alcohols Mainly conventional OXO alcohol and modified primary OXO alcohol + trace paraffin free Modified Primary OXO Alcohol Linear OXO Alcohol 65 Mixtures in Paraffins of Modified Primary OXO Alcohols and Regular OXO Alcohols Predominantly linear paraffin and methyl-branched paraffin plus up to about 25% conventional OXO alcohol (primary OXO alcohol type formed from OXO reaction on linear feedstock) and modified primary OXO alcohol b-paraffin l-paraffin-modified primary OXO alcohol linear OXO alcohol 66 Mixture in paraffins of mixtures of modified alkylbenzenes and linear alkylbenzenes Predominantly linear paraffins and methyl-branched paraffins + up to about 30% linear alkylbenzenes and modified alkylbenzenes b-paraffin-paraffin-modified alkylbenzenel-alkylbenzene

The hydrocarbon feeds exemplified in the above table are, of course, presented by way of example and should not be taken as limiting the invention. Any other suitable hydrocarbon feed can be used. For example, it is a decomposition product of petroleum wax including a decomposition product of Fischer-Tropsch wax. These waxes are derived from lubricating oil distillates and melt in a relatively low range up to about 72 ° C., for example in the range from about 50 to about 70 ° C., and contain from about 18 to about 36 carbon atoms. Such waxes preferably contain 50 to 90% of normal alkanes and 10 to 50% of monomethyl branched alkanes and small amounts of various cyclic alkanes. Such digest products are particularly useful in alternative embodiments of the present invention, as described in further detail below, and are described in the literature ("Chemical Economics Handbook", published by SRI (Menlo Park, California) and "Waxes"", S595.5003 L, published 1995]. Paraffin waxes are also described in Kirk Othmer's Encyclopedia of Chemical Technology, 3 ^rd . Edition, (1984), Volume 24 and "Waxes", page 473. Also derived from, for example, Fischer-Tropsch synthesis, having any equivalent alternative hydrocarbon feed or more preferably a shorter chain equivalent in the C10-C20 range and a significant monomethyl-branch at any position in the chain. Suitable.

The hydrocarbon feed herein may contain varying amounts of N, O, S impurities. If certain preferred hydrocarbon feeds are particularly derived from sulfur- and / or nitrogen-containing fractions, they are desulfurized and / or liberated from nitrogenous materials using conventional desulfurization or “de-NOS” techniques.

The hydrocarbon feed herein is used prior to use in the process of the present invention such that the maximum amount of hydrocarbons having a particular chain length and / or branching degree is used most effectively to produce modified alkylbenzenes and / or modified primary OXO alcohols. Can be separated. For example, although not specifically shown in the figures, each process includes an alkylation step to form a modified alkylbenzene as described herein, and a process comprising an OXO step to form a modified OXO alcohol. It may be desirable to use two paraffinic distillates from kerosene for two essentially parallel processes. In this binary process, a heavier distillate, such as a distillate having an overall lower carbon number (e.g., a distillate enriched in C11-C13 hydrocarbons) is used to prepare the modified alkylbenzene, for example It may typically be desirable to use a distillate enriched in C14-C17 hydrocarbons to produce a modified OXO alcohol. Other process modifications include the use of multiple hydrocarbon streams or distillates to simultaneously produce modified and non-modified (normal) alkylbenzenes and / or OXO alcohols.

Adsorptive separation step (s)

In general, the separation technique in step (a) or step (A) of the process of the invention relies on the adsorption of porous media layers and / or the use of inclusions. Labeled patents for adsorptive separation are generally US Pat. No. 2,985,589, which describes apparatus, adsorbent layers, and process conditions of temperature and pressure suitable for use herein. '589 does not describe conclusive modifications, in particular the connection of pore sizes and steps for specific separations that are part of the present invention.

The adsorptive separation step herein may generally be carried out in the vapor phase or in the liquid phase and may or may not use any commercial process equipment as indicated in the background of the present invention.

Porous media used as adsorbents generally dry or do not dry. Preferred embodiments include those in which the adsorbent is dried to contain less than about 2% free moisture.

Any adsorptive separation step according to the invention may or may not use a desorbent or a substituent. In general, any desorption means such as pressure-swing or other means can be used. However, preferably using such a desorbent, that is, solvent substitution is a preferred method of desorbing the stream from the porous medium used herein. Suitable desorbents or substituents include low molecular weight n-paraffins such as heptane or octane, or polar desorbents such as ammonia. Regardless of their presence, fully conventional well known desorbents are not explicitly included in representing any streams or their compositions in the process of the present invention, and desorbent recycling steps not explicitly shown in FIGS. Of course, it can be recycled freely.

In the method of the present invention, step (a) may use the MOLEX ^R process step of UOP, and the method of the present invention is performed once using a porous material having a larger pore than the conventional 5Å zeolite used in the linear alkylbenzene preparation process. There is a difference that must include the above adsorptive separation step. MOLEX ^R is discussed in the above document. Surfactant Science Series Vol. 56, for example, pages 5-10]. Vapor phase processes, such as the IsoSiv process (Union Carbide (see same document)) are also useful but less preferred.

The apparatus and operating conditions for any version of the MOLEX ^R process used herein are well known and refer to, for example, page 9 of the document shown above, which shows a process comprising in detail raffinate and adsorbent and various streams thereof. do.

Porous media (larger-pore type)

The porous medium required for step (a) or step (A) herein is a larger-pore type. “Larger-voids” are specifically large enough to hold monomethyl-branched linear olefinic or paraffinic hydrocarbons and dimethyl-branched or trimethyl-branched linear olefinic or paraffinic hydrocarbons that are not co-phase dimethyl hydrocarbons. On the other hand, it refers to a porous material having pores small enough to partially or wholly exclude cyclic (e.g., 5- or 6-membered rings) and aromatic hydrocarbons, as well as hydrocarbons branched into isomeric dimethyl, ethyl and higher higher alkyls. do. Such pore sizes large enough to hold a significant amount of methyl-branched hydrocarbons are not always used in conventional linear alkylbenzene preparations and are generally much higher in any commercial process than the more conventional 4-5 mm pore size zeolites. More rarely used. Larger-porous porous media are those used in the adsorptive separation apparatus indicated as “SOR 5/7” in FIGS. 1 to 7.

Thus, the porous medium necessary for step (a) or step (A) herein is larger than the pore size required for the selective adsorption of linear acyclic hydrocarbons, i.e. the minimum that exceeds the pore size used in conventional linear alkylbenzene preparations. Having a pore size, the pore size does not exceed about 20 mm 3, more preferably about 10 mm 3, and very preferably averages about 5 to about 7 mm 3. When specifying the minimum pore size for so-called “large-pore” porous materials herein, it should be recognized that such materials often have elliptical pores, for example, the pore size of SAPO-11 is 4.4 × 6.7. 평균 (mean 5.55 Å) [S. Miller, Microporous Materials, Vol. 2., pages 439-449 (1994). When comparing these materials with “smaller-pore” zeolites, such as 4-5 microns homogeneous-pore zeolites, the present application is to determine the mean or larger elliptical dimension of the elliptical dimension when comparing the size—not any smaller elliptical dimension. Promise in. Thus, the SAPO-11 material as defined herein has a larger pore size than 5 kPa homogeneous-pore zeolites.

The porous medium having the larger voids necessary for step (a) or step (A) herein may be zeolite (aluminosilicate) or non-zeolite.

Suitable non-zeolites may be silicoaluminophosphate, in particular SAPO-11, but other silicoaluminophosphates, for example when present in one or more elliptical dimensions with an average pore size of at least about 5 mm 3 or an elliptic pore greater than 5 mm 3 For example, SAPO 31 or 41 can be used.

Another suitable technique for adsorptive separation herein is to use pyrolyzed poly (vinylidene chloride), ie pyrolyzed SARAN prepared for example according to Dutch patent application NL 7111508 (published October 25, 1971). Adsorption. Preferred materials have a sieve diameter of 4 to 7 mm 3. When such materials are used as essential adsorbents, pore sizes of about 5 mm 3 or more are used.

Use of organometal-grafted mordenite and other grafted zeolites as porous medium in step (a) or step (A)

The present invention also encompasses particularly useful embodiments wherein the adsorptive separation of step (a) or step (A) comprises at least one separation step using organometal-grafted mordenite. Particularly suitable as "large-pore" porous media herein are grafted mordenites, such as tin-grafted mordenites. Likewise, and more generally, the present invention provides a method comprising the use of grafted mordenite for preparing a cleaning surfactant and any corresponding surfactant, and by using these specific porous media in any of the methods described above. Consumable products produced (see EP 559,510 A (9/8/93), incorporated herein by reference in its entirety). The practitioner will select the grafted mordenite of EP 559,510 which is most suitable for separating linear and monomethyl-branched hydrocarbons from isophase dimethyl and polymethyl hydrocarbons which can be clearly identified from the examples thereof.

Other grafted zeolites useful as the porous media herein also include those of US Pat. No. 5,326,928, which is incorporated herein by reference in its entirety. In this aspect of the invention, incorporation into a single process using both the grafted mordenite described above in step (a) and H-mordenite partially or wholly dealuminated in the alkylation step (c) as defined herein. It is especially preferable to make it.

Based on this, using the terminology of US Pat. No. 5,326,928, which describes a process module containing grafted components, in combination with the preferred alkylation steps as defined herein, the present invention also provides modified alkylbenzenes and And / or a process for producing a modified alkylbenzenesulfonate, which process comprises: (a) obtaining a void for selectively introducing a lesser branched paraffin without introducing a hydrocarbon charge and a more branched paraffin; Is separated by contacting at least one adsorbent layer comprising at least one microporous solid (as defined in U.S. Pat. Less branched aliphatic paraffins with varying degrees of branching in 14 hydrocarbon fillers (line And one or more first effluents comprising monomethyl, optionally certain dimethyl-branched) paraffins and one or more agents comprising more branched paraffins (trimethyl and highly-branched paraffins and optionally cyclic and / or aromatic impurities). At least one step of separating into two effluents; (b) the less branched effluent of step (a), more preferably partially or wholly dealuminized, partially or wholly acidic H-mordenite, preferably with an internal isomeric selectivity of 0 to 40 At least one alkylation using as catalyst; And (c) one or more steps of sulfonating the product of step (b) using any conventional sulfonating agent. The resulting modified alkylbenzenesulfonic acid can be neutralized and incorporated into the cleaning article as taught herein.

In step (a) or step (A) of the process of the invention, it is desirable to use zeolites or other porous media in a form in which they do not actively promote the chemical reaction of the feedstock, for example, do not pyrolyze and polymerize. desirable. Thus, acidic mordenite is preferably avoided in step (a) or step (A). The acidic form is preferred, in part or in whole, as opposed to subsequent alkylation catalysts.

Porous Medium (less-pore type)

For example, the smaller-porous zeolites optionally useful in step (a) or step (A) used in a process such as in an adsorptive separation apparatus shown as " SOR 4/5 " in FIGS. 1, 2, 5, 6, etc., Selective adsorption of linear hydrocarbons and no significant adsorption of methyl-branched hydrocarbons. Such porous materials are well known and include, for example, calcium zeolites having 4 to 5 GPa pores. Such materials are further described in US Pat. No. 2,985,589 and are currently commercially used in the preparation of linear alkylbenzenes.

Porous media (eg OLEX ^R Or similar process)

When preparing the modified primary OXO alcohols herein, it may be desirable to concentrate the mono-olefins by performing an olefin / paraffin separation step in step (C). Reference is made to "SOR O / P" in the drawing and in step (C) within the claims. Suitable porous media for this step include copper- or silver-treated zeolite X or zeolite Y. See, eg, US Pat. No. 5,300,715 or US Pat. No. 4,133,842, and references cited therein. See also US Pat. No. 4,036,744 and US Pat. No. 4,048,111. Alternatively, Technology Licensor (UOP Corp.) includes the entire process known as OLEX ^R available for approval.

Inclusion

Urea inclusions can also be used in step (a) to separate n-paraffins from branched paraffins and are well known in the art. Surfactant Science Series, Marcel Dekker, N.Y., 1996, Vol. 56, pages 9-10 and references cited therein: "Detergent Manufacture Including Zeolite Builders and other New Materials, Ed. Sittig., Noyes Data Corp., 1979, pages 25-30, and especially chlorocarbon solvents using solid urea US Patent No. 3,506,569, which is incorporated by reference in its entirety, which is not used at all .. More generally but less preferably, a process according to US Patent No. 3,162,627 may be used.

Dehydrogenation

In general, the dehydrogenation of olefins or olefin / paraffin mixtures in the process of the present invention is described in the references cited in the background, Surfactant Science Series and “Detergent Manufacture Including Zeolite Builders and other New Materials, Ed. Sittig., Noyes”. Data Corp., New Jersey, 1979] can be carried out using well known dehydrogenation catalyst systems including other dehydrogenation catalyst systems such as those commercially available from UOP Corporation. Can be carried out in the presence of hydrogen gas, and typically noble metal catalysts (eg DeH-5 ^R , DeH-7 ^R , DeH-9 ^R (sales UOP)) are present in place of non-hydrogen, zeolite / air Precious metal free dehydrogenation systems such as systems can be used in the absence of precious metals.

More specifically, dehydrogenation catalysts useful herein are supported on Sn-containing alumina as described in US Pat. No. 5,012,027, which is incorporated by reference, and contains Pt 0.16%, Ir 0.24%, Sn 0.50%, and Li 0.54. Catalysts containing%. When contacted with a C9-C14 paraffin mixture (which is considered to be linear) at 500 ° C. and 0.68 atm, this catalyst produces an olefinic product (38 h on stream) with a selectivity of 90.88% and a conversion of 11.02%. Is considered very suitable for partially or totally dehydrogenation of branched hydrocarbon-enriched streams of paraffins in US Pat. No. 4,786,625; EP 320,549 A1 (6/21/89); Vora et al., Chem. Age India (1986), 37 (6), 415-18].

As mentioned above, dehydrogenation can be whole or partial, more typically partial. In part, this step forms a mixture of the olefin (eg, about 10%, but this is only an example and should not be considered limiting) and the remaining unreacted paraffins. This mixture is a suitable feed for the alkylation step of the present invention.

Other useful dehydrogenation systems that are readily employed in the present invention are dehydrogenation catalysts having a modifier metal selected from the group consisting of Sn, Ge, Re and mixtures thereof, alkali metals, alkaline earth metals or mixtures thereof and especially defined heat resistant oxide supports. A dehydrogenation system of US Pat. No. 4,762,960, which is incorporated by reference describing Pt group metals containing.

Alternative dehydrogenation catalysts and conditions useful herein include those of US Pat. No. 4,886,926 and US Pat. No. 5,536,695.

Alkylation

An important aspect of the present invention further includes delinearization by separative concentration of slightly branched paraffins and alkylation which occurs after partial or total dehydrogenation of the delinearized olefins or olefin / paraffin mixtures. Alkylation is carried out using aromatic hydrocarbons selected from benzene, toluene and mixtures thereof.

Internal Isomer Selectivity of the Alkylation Step and its Selection

Preferred embodiments of the process of the invention require an alkylation step with an internal isomer selectivity of 0-40, preferably 0-20, more preferably 0-10. Internal isomer selectivity as defined herein, ie “IIS”, is determined by performing an alkylation test of benzene with 1-dodecene at a molar ratio of 10: 1 for all given alkylation process steps. Alkylation is carried out in the presence of an alkylation catalyst such that the dodecene conversion is at least about 90% and the monophenyldodecane formation is at least about 60%. The internal isomer selectivity is then measured as follows:

IIS = 100 * [1- (final amount of phenyldodecane) / (total amount of phenyldodecane)]

Wherein the amount is based on the weight of the product, the amount of final phenyldodecane is the sum of 2-phenyldodecane and 3-phenyldodecane, and the total amount of phenyldodecane is 2-phenyldodecane, 3- Phenyldodecane, 4-phenyldodecane, 5-phenyldodecane, and 6-phenyldodecane combined, these amounts being determined by all known analytical techniques for alkylbenzenesulfonates 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". When calculating IIS according to the above equation, you need to divide the above amount and then subtract the result from 1 and multiply by 100. Of course, the particular alkene used to characterize or test all suitably provided alkylation steps compares the alkylation step of the present invention to known alkylation steps as used to prepare linear alkylbenzenes and allows the practitioner of the present invention to It is a reference material that allows one to determine whether or not an alkylation step is useful in the context of a series of process steps that make up the present invention. In the process of the invention as carried out, the actual hydrocarbon hydrocarbon feedstock used is of course as specified on the basis of the preceding process steps. In addition, as noted above, all current commercial processes for making LAS exclude from preferred embodiments of the present invention based solely on IIS for the alkylation step. For example, LAS processes based on aluminum chloride, HF and the like have IIS outside the scope specified in the present invention. Alternatively, several alkylation steps, which are known in the literature but not applicable to current commercial alkylbenzenesulfonate preparations, are useful in the present invention as they have suitable IIS.

More specific examples of IIS measurements are given below to assist the performer in measuring IIS and determining whether a given alkylation process step is suitable for the present invention.

As described above, the alkylation test of benzene with 1-dodecene is carried out at a molar ratio of benzene: 1-dodecene of 10: 1, wherein the alkylation is at least 90% conversion of dodecene in the presence of an alkylation catalyst and mono It is carried out so that the formation rate of phenyldodecene is at least 60%. The alkylation test should generally be carried out for a reaction time of less than 200 hours at a reaction temperature of about −15 to about 500 ° C., preferably about 20 to 500 ° C. The pressure and catalyst concentration for 1-dodecene can vary widely. No solvent other than benzene is used in the alkylation test. The process conditions used to determine the IIS for the catalyst or the alkylation step may be based on the literature. The practitioners will generally use appropriate conditions based on large data sets that are fully documented for alkylation. For example, suitable process conditions for determining whether AlCl ₃ alkylation can be used in the present invention are illustrated by reacting 5 mol% of AlCl ₃ with respect to 1-dodecene in a batch reactor at 20-40 ° C. for 0.5-1.0 hour. do. This test demonstrates that the AlCl ₃ alkylation step is not suitable for use in the present invention. About 48 IISs should be obtained. In another example, a suitable alkylation test using HF as a catalyst should provide about 60 IIS. Thus, neither AlCl ₃ alkylation nor HF alkylation fall within the scope of the present invention. For zeolites with medium porosities, such as dealuminated mordenite, suitable process conditions for measuring IIS are reactions of about 200 ° C. with 1-dodecene and benzene at a WHSV of 30Hr ⁻¹ at a molar ratio of 10: 1. Illustrated by passing the mordenite catalyst at a temperature and a pressure of about 200 psig, in which case the IIS for the mordenite catalyst should be about zero. Temperatures and pressures for exemplary mordenite alkylation tests (see specific examples of the present invention below) are expected to be more generally useful for zeolites and other form-selective alkylation catalysts. When using a catalyst such as H-ZSM-4, about 18 IIS should be obtained. Clearly, dealuminated mordenite and H-ZSM-4 catalyzed alkylation provide IIS suitable for the present invention, with mordenite being better.

Without being bound by theory, the low-IIS alkylation step carried out using H-mordenite alkylates benzene into branched hydrocarbon-rich hydrocarbons and also very usefully locates the methyl side chains attached to the hydrocarbon chain. It is considered to be able to scrambling.

Alkylation catalyst

The IIS required in the alkylation process step can be carried out by precisely controlling and selecting the alkylation catalyst. Many alkylation catalysts are readily determined to be unsuitable. Unsuitable alkylation catalysts include DETAL ^R process catalysts, aluminum chloride, HF, HF on zeolites, fluoride zeolites, non-acidic calcium mordenites and many others. In fact, in the commercial preparation of linear alkylbenzenesulfonate detergents, it has now been found that any alkylation catalysts used for alkylation are not suitable.

In contrast, suitable alkylation catalysts for the present invention are selected from form-selective and suitably acidic alkylation catalysts, preferably zeolites. In such catalysts for the alkylation step (step (b)) the zeolite is preferably with mordenite, ZSM-4, ZSM-12, ZSM-20, opriteite, ghelliniite and zeolite beta, which are in part or in whole acid form. It is selected from the group consisting of. More preferably, the zeolite of step (b) (alkylation step) is substantially in acid form, with a conventional binder and additionally at least about 0%, more preferably at least 5%, more typically 50 to about 90% It is contained in catalyst pellets containing zeolites.

More generally, suitable alkylation catalysts do not include binders or other materials used to form catalyst pellets, aggregates or composites, and are usually partially or wholly crystalline and more preferably substantially crystalline. In addition, the catalyst is typically partly or wholly acidic. For example, fully exchanged Ca type mordenite is not suitable, while H type mordenite is suitable. These catalysts are then useful for the alkylation step, which is defined as step (b) in the claims: they correspond to step 7 of FIG. 1.

The pores characterizing the zeolites useful in the alkylation process of the present invention may be substantially circular, such as kancleanite, having a uniform pore of about 6.2 kPa, and may preferably be somewhat elliptical, such as in mordenite. In any case, the zeolites used as catalysts in the alkylation step of the present invention may be characterized by the pore dimensions of zeolites having large pore sizes such as X zeolites and Y zeolites, and the pore dimensions of ZSM-5 and ZSM-11 having relatively small pore sizes. Of course, it has a moderate pore size, preferably about 6 to about 7 mm 3. In fact, testing of ZSM-5 proved unusable in the present invention. The pore size and crystal structure of certain zeolites are described in ATLAS OF ZEOLITE STRUCTURE TYPES, WM Meier and DH Olson, published by the Structure Commission of the Internatinal Zeolite Association (1978 and more recent editions) and distributed by Polycrystal Book Service, Pittsburgh , Pa].

Zeolites useful in the alkylation step of the process of the invention are generally filled with at least 10% of their cationic moieties with ions other than alkali or alkaline earth metals. Typical but non-limiting common replacement ions include ammonium, hydrogen, rare earth metals, zinc, copper and aluminum. Of these groups, ammonium, hydrogen, rare earth metals or combinations thereof are particularly preferred. In a preferred embodiment, the zeolite is mainly converted to the hydrogen form by replacing the alkali metal or other ions originally present with a hydrogen ion precursor, for example ammonium ions, wherein the conversion is followed by calcination to obtain the hydrogen form. This exchange is usually accomplished by contacting the zeolite with an ammonium salt solution, such as ammonium chloride, using well known ion exchange techniques. In certain preferred embodiments, at least 50% of the cationic moiety is replaced to produce a zeolitic material filled with hydrogen ions.

Zeolites are treated by various chemical treatments, including alumina extraction (dealuminization) and combination with one or more metal components, in particular Group IIB, III, IV, VI, VII and VIII metals. In some cases, it is also contemplated that heat treatment, including deposition or calcining of zeolites in air, hydrogen or an inert gas such as nitrogen or helium, is preferred.

Suitable reforming treatments involve depositing the zeolite by contacting the zeolite with an atmosphere containing from about 5 to about 100% steam at a temperature of about 250 to 1000 ° C. Deposition can last for about 0.25 to about 100 hours and can be performed under partial vacuum to several hundred pressures.

In carrying out the preferred alkylation step of the process according to the invention, a crystalline zeolite having a medium pore size as described above is applied to a matrix that is resistant to other materials, for example binders or other conditions used in temperature and processing. Incorporation can be useful. Such matrix materials include synthetic or natural components as well as inorganic materials such as clays, silicas and / or metal oxides. The matrix material may be in the form of a gel including a mixture of silica and metal oxides. The latter case may be natural or in the form of a gel or gelled precipitate. Natural clays that can be mixed with zeolites include those of the montmorillonite and kaolin series, which include a-bentonite, and kaolin, commonly known as Dixie, McNamee-Georgia, and Florida clay, Or other materials whose main inorganic components are halosite, kaolinite, dickite, nacrite or anoxite. These clays can be used as raw, such as first mined, or initially calcined, acid treated or chemically modified.

The medium pore size zeolites used in the present invention can be used in addition to the above-mentioned materials, as well as porous matrix materials such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-toria, silica-berilia and silica-titania, as well as silica- It may be mixed with ternary blends such as alumina-toria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix may be in the form of a cogel. The relative amounts of the finely divided zeolite and inorganic oxide gel matrix can vary widely and the zeolite content ranges from about 1 to about 99 weight percent, more typically from about 5 to about 80 weight percent, based on the weight of the composite. to be.

The silica: alumina ratio of the zeolite group comprising several zeolites useful for the alkylation step herein is at least 10: 1, preferably at least 20: 1. In this specification, the silica: alumina ratio refers to the structure or structure ratio, ie the ratio of SiO ₄ to tetrahedral AlO ₄ . This ratio may vary depending on the silica: alumina ratio measured by various physicochemical methods. For example, the overall chemical analysis may include aluminum present in the form of a cation that binds to the acidic sites on the zeolite, resulting in a low silica: alumina ratio. Similarly, when this ratio is measured by thermal gravity analysis (TGA) of ammonia desorption, small amounts of ammonia can be titrated if the cationic aluminum prevents the exchange of ammonium ions to acidic sites. This imbalance is particularly problematic when using certain treatment methods, such as the dealumination method described below, which produces ionic aluminum that does not have a zeolite structure. Therefore, care must be taken to accurately measure the silica: alumina structure ratio.

Zeolite beta (but less preferred than H-mordenite) suitable for use herein is described in US Pat. No. 3,308,069, which documents these zeolites and methods for their preparation in detail. Such zeolites in acid form are also commercially available as Zeocat PB / H from Zeochem.

When preparing zeolites in the presence of organic cations, the zeolites are catalytically inert, since the voids in the crystals can be filled with organic cations from the formed solution. They can be activated by heating to 540 ° C. for 1 hour in an inert atmosphere, followed by base exchange with, for example, ammonium salts and then calcining at 540 ° C. in air. The presence of organic cations in the solution formed may not necessarily be necessary for the formation of the zeolite, but appears to be advantageous for forming this particular type of zeolite. Some natural zeolites can sometimes be converted to the desired type of zeolite by various activation processes and other treatments such as base exchange, deposition, alumina extraction and calcination. The zeolite preferably has a crystal structure density of at least about 1.6 g · cm ⁻³ in the anhydrous hydrogen form. Anhydrous densities of known structures are described in page 19 of the article on Zeolite Structure by WM Meier included in "Proceedings of the Conference on Molecular Sieves, London, April 1967", published by the Society of Chemical Industry, London, 1968. ] it can be calculated from, 1000Å ³ the number of silicon atoms per + aluminum atoms, as set out in. The above references discuss the crystal structure density. US Pat. No. 4,016,218, which is incorporated by reference, further discusses the values for some common zeolites with crystal structure density. When zeolites are synthesized in alkali metal form, the zeolites are typically converted to hydrogen form by forming an ammonium form intermediate as a result of ammonium ion exchange and calcining the ammonium form to obtain a zeolite in hydrogen form. Although zeolites in the hydrogen form successfully catalyze the reaction, it has been found that the zeolites may also be in part in the form of alkali metals.

EP 466,558 has an atomic ratio of total Si / Al of 15 to 85 (15 to 60), a Na weight content of less than 1000 ppm (preferably less than 250 ppm) and a low or zero content of the external network Al species. An acidic mordenite type alkylation catalyst is described which can also be used herein as the mesh volume is 2760 nm ³ .

U.S. Pat.No. 5,057,472 discloses preferably 0.5 to 3 (preferably containing an NH ₄ NO ₃ sufficient to completely exchange Na ions with NH ₄ and H ions for acid-stable Na ion-containing zeolites, preferably mordenite). Relates to the simultaneous dealumination and ion exchange of the zeolites carried out by contact with a 1 to 2.5) M HNO ₃ solution, which is useful for preparing the alkylation catalysts of the present invention. The SiO ₂ : Al ₂ O ₃ ratio of the resulting zeolite is 15 to 26 (preferably 17 to 23): 1 and is preferably calcined to convert the NH ₄ / H form partially or wholly into the H form. Optionally, although not particularly preferred in the present invention, the catalyst may contain a Group VIII metal (and optionally an inorganic oxide) together with the calcined '472 zeolite.

Another acidic mordenite catalyst useful in the alkylation step of the present invention is described in US Pat. No. 4,861,935, which relates to a hydrogen form mordenite incorporating alumina, a composition having a surface area of at least 580 m 2 / g. Other acidic mordenite catalysts useful in the alkylation step of the present invention include those catalysts described in US Pat. No. 5,243,116 and US Pat. No. 5,198,595. U. S. Patent No. 5,175, 135 discloses another alkylation catalyst useful in the present invention having a silica / alumina molar ratio of at least 50: 1, a symmetry index measured by X-ray diffraction analysis of at least 1.0, and a total pore volume. Acid mordenite zeolites having a porosity of about 0.18 to about 0.45 cc / g and having a combined volume ratio of mesopores and macropores to total pore volume of about 0.25 to about 0.75 are described.

Particularly preferred alkylation catalysts herein include the acidic mordenite catalyst Zeocat ™ FM-8 / 25H from Zeochem, CBV 90 A from Zeolyst International and LZM-8 from UOP Chemical Catalysts.

Most generally, any alkylation catalyst may be used in the present invention as long as the alkylation step meets the internal isomer selectivity requirements defined above.

Distillation of Modified Alkylbenzene or Modified Primary OXO Alcohols

Optionally, according to the exact order of the feedstock and the steps used, the process of the present invention comprises the steps of distilling the modified alkylbenzene or the modified primary OXO alcohol to remove unreacted starting materials, paraffins, excess benzene and the like. It may include. All conventional distillation apparatus can be used. The general procedure is similar to that used to distill conventional linear alkylbenzenes (LABs) or modified primary OXO alcohols. Suitable distillation steps are described in the Surfactant Science Series, for example the review of alkylbenzensulfonate manufacture.

Sulfonation / Sulfation and Post Treatment

In general, sulfonation of modified alkylbenzenes or sulfonation of modified primary OXO alcohols in the process of the present invention is described in the above-mentioned "Detergent Manufacture Including Zeolite Builders and Other New Materials" and Surfactant Science Series review of alkylbenzensulfonate. can be achieved using all well-known sulfonation systems, including the methods described in manufacture. Common sulfonation systems include sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide, and the like. Sulfur trioxide / air is particularly preferred. Sulfonation with suitable air / sulfur trioxide mixtures is described in detail in US Pat. No. 3,427,342 to Chemithon. Sulfonation processes are described more extensively in the literature. See, "Sulfonation Technology in the Detergent Industry", W.H. de Groot, Kluwer Academic Publishers, Boston, 1991].

All conventional workup steps can be used in the process of the invention. A common procedure is to sulfonate and then neutralize with a suitable alkali. Thus, the neutralization step can be carried out using an alkali selected from sodium, potassium, ammonium, magnesium and substituted ammonium alkalis and mixtures thereof. Potassium aids in solubility, magnesium promotes softening performance, and substituted ammonium can help formulate certain variants of the surfactants of the invention. The present invention relates to modified alkylbenzenesulfonate surfactants, or sulfated modified primary OXO alcohols, or all derivatives of alkoxylated, sulfated modified primary OXO alcohols, as prepared by the process of the present invention. Form and use thereof in consumer product compositions.

Alternatively, the acid form surfactants of the present invention may be added directly to an acidic cleaning article or mixed with the cleaning components and then neutralized.

Post-alkylation step

As mentioned above, the process for producing modified alkylbenzenes herein includes embodiments comprising the steps following the alkylation step (c). These steps preferably comprise (d) sulfonating the product of step (c); And (e) neutralizing the product of step (d) and mixing (f) the product of step (d) or (e) with at least one cleaning product aid to form a cleaning article.

Blending aspect

In one preferred embodiment, prior to the sulfonation step, the modified alkylbenzene which is the product of step (c) is blended with the linear alkylbenzene prepared by conventional processes. In another embodiment, in any step subsequent to this sulfonation step, the modified alkylbenzene sulfonate, the product of step (d), is blended with the linear alkylbenzene sulfonate prepared by conventional processes. In this blending embodiment, the preferred method has a ratio of modified alkylbenzene: linear alkylbenzene from about 10:90 to about 50:50.

In addition, the corresponding blending schemes are of course applicable to the modified primary OXO alcohol process herein. In addition, any blend may be prepared with the different types of surfactants herein, or precursors thereof. For example, the operator can freely blend the modified alkylbenzene with an alkoxylated mixture using a modified primary OXO alcohol and ethylene oxide, propylene oxide, etc., as prepared herein, and then sulfate / sulfurize the resulting mixture. Can be fonned. Also, in general, the present invention is also subject to any modified or branched modified obtainable herein, since modified OXO alcohols can be separated by distillation, and various other OXO alcohols, including linear OXO alcohol types, are known in the art. OXO alcohols in any ratio with any known linear OXO alcohol, for example, branched OXO alcohol: linear OXO alcohol from about 1: 100 to about 100: 1, and such OXO alcohol blend is detergent To a surfactant useful for the process.

Other Process Aspects

The present invention is also characterized in that the separation comprises (i) at least one step which is essential in the process for the preparation of linear alkylbenzenes selected from separation by inclusion and adsorption by urea, thereby reducing the normal paraffin concentrated stream and isoparaffin. Separating at least partially isoparaffin into an effluent stream having an isoparaffin (particularly methyl branched paraffin) concentrated stream comprising at least 10% and having a molecular weight of at least about 128 and up to about 282; (ii) addition or subsequent to step (i), partially or fully further concentrating the isoparaffin content of the effluent stream by at least one step selected from urea inclusion and adsorptive separation; And (iii) partially or wholly dehydrogenating the isoparaffin concentrated stream of step (ii), to obtain an effluent stream from a linear alkylbenzenesulfonate surfactant useful for cleaning articles.

More generally, the hydrocarbons produced herein are expected to be useful in modified alkylbenzenesulfonate surfactants as exemplified herein without limitation, as well as in modified surfactants other than alkylbenzenesulfonate (eg, alkyl sulfates). do. Thus, the present invention is also characterized in that the separation comprises at least one step selected from separation by inclusion and adsorption by urea, (i) isoparaffin containing at least about 10% of a normal paraffin concentrated stream and isoparaffin. Partially or totally separating isoparaffin into an effluent stream in the form of a paraffin concentrated stream; (ii) addition or subsequent to step (i), partially or fully further concentrating the isoparaffin content of the effluent stream by at least one step selected from urea inclusion and adsorptive separation; And (iii) partially or totally dehydrogenating the isoparaffin enriched stream of step (ii), to obtain a branched paraffinic effluent stream.

In such embodiments, the isoparaffin-enriched stream may vary in total carbon content from about C10 to about C20, and the nonlinear distillate of the concentrated stream averages about 1 to about methyl side chains rather than terminal methyl side chains per molecule. The nonlinear distillate of the two, further concentrated stream preferably contains less than about 30%, more preferably less than about 10%, even more preferably less than about 1% of molecules having quaternary carbon atoms and , Less than 50%, preferably less than about 10%, more preferably less than about 1%, of the same elemental dimethyl substituted molecule.

Process embodiment incorporating hydroformylation (OXO reaction)

As described above in the Summary of the Invention, the present invention also provides novel and useful modifications that can be used to produce hydrocarbons, soluble sulfates, poly (alkoxy) sulfates, and poly (alkoxylates) that are highly soluble by the particular adsorptive separation method selection. A process embodiment comprising converting to a primary OXO alcohol. These are just examples. Modified forms of other surfactant types known in the art, derivable from OXO alcohols, are of course included in the present invention. With respect to this process embodiment as roughly defined in the summary of the invention, the preferred process herein comprises at least one device and at least two layers in which step (A) at least one of the methyl-branched acyclic aliphatic hydrocarbons Comprising a porous medium that is distinguished by comparison to the porous medium content of another layer by enhanced performance). Also preferably, step (D) comprises a one step OXO step wherein the OXO catalyst is a phosphine-coordinated transition metal other than iron.

More specifically, in this preferred process, at least one layer comprises a porous medium customary for the preparation of linear alkylbenzenes, wherein the at least one layer is methyl-branched in a stream delivered to step (B) in the process. Suitable for increasing the ratio of the acyclic aliphatic hydrocarbons added in part or in whole, and the ratio of the linear acyclic aliphatic hydrocarbons (partly removed as linear hydrocarbon-rich streams in step (A)) delivered to step (B) in the process. This leads to a process suitable for reducing both partially and totally.

Typically, in this process embodiment, the simulated moving bed adsorptive separation in step (A) comprises one device capable of simulating the migration of porous media in two or more of the one or more layers; Or two or more devices.

In addition, there are two of the one or more layers, each of which comprises different members of the porous medium, each layer being controlled by one device, each device achieving simulated movement of the porous medium in the one or more layers. Included in the present invention is a process comprising at least eight ports for. For example, see FIG. 9 where device SOR 4/5 comprises a specific type of porous medium as defined in more detail elsewhere herein, and device SOR 5/7 includes another type. The mentioned "apparatus" may be selected from particular rotary valve devices, in particular as described in detail in several patents identified in the "Background" section. Furthermore, although more particularly illustrating a process comprising an alkylation step, reference is made in detail to FIG. 8, which shows an adsorptive separation device, a rotary valve and an accessory device. Therefore, the selection of the device and its connection method, which is essential for the purpose of the present invention to complete the device, adsorption medium and equipment, to be precisely better OXO alcohols and derived surfactants, are of course all individually known.

Thus, the present invention also provides that a linear hydrocarbon-rich stream is present in step (A), wherein step (A) (A) adsorbs the hydrocarbon feed into a linear hydrocarbon-rich stream and an intermediate branched hydrocarbon-rich stream, Withdrawing the linear hydrocarbon-rich stream by simulated moving bed adsorptive separation means; And (A-ii) branched hydrocarbons comprising acyclic aliphatic hydrocarbons branched at an increased rate relative to the intermediate branched hydrocarbon-rich streams by intermediate simulated moving bed adsorptive separation means. And a type of OXO-alcohol preparation process comprising adsorbing to a concentrated stream and an outlet stream comprising cyclic and / or aromatic hydrocarbons at least in an increased proportion relative to the branched hydrocarbon-rich stream.

Preferably, in this embodiment, all the layers are not customary in the preparation of linear alkylbenzenes and the methyl-branched acyclic aliphatic in the stream whose pore size is suitable for the process and is passed to step (B) in the process. Partially or totally increase the ratio of hydrocarbons and linear acyclic aliphatic hydrocarbons, and partially or totally increase the proportion of aliphatic hydrocarbons branched into cyclic, aromatic and / or ethyl or higher higher alkyls delivered to step (B) in the process. A porous medium (eg, SAPO—, connected to the process in a manner suitable for reduction, wherein hydrocarbons other than the linear- and methyl-branched hydrocarbons are partially or wholly removed as effluent streams in step (A). 11 containing device SOR 5/7 or larger pore size than used to prepare linear alkylbenzenes Other equivalent molecular sieves).

Suitably, in the OXO-alcohol preparation embodiment of the invention, the hydrocarbon feed comprises at least about 10% methyl-branched paraffins having a molecular weight of about 128 to about 282. See the tables in other parts of this application for further description of suitable feeds.

The crude feed in the OXO-alcohol process herein is preferably distilled before use. For example, but not limited to, by a distillation apparatus at the beginning of the process shown in FIGS. 9 to 18. In this example, the hydrocarbon feed comprises up to about 3 carbon atoms (preferably up to about 2 carbon atoms) in the C10 to C17 range (as it proceeds from the distillation apparatus to the rest of the process). Such distillate may be a one-carbon distillate, a two-carbon distillate, a three-carbon distillate, or a distillate comprising an inaccurate range of carbon number, for example, 1½-carbon distillate. Examples of suitable distillates further include C11-C13 distillates, C14-C15 distillates and C15-C17 distillates, but are not intended to exclude other distillates such as C16.5 distillates. Distillates represented by non-integer carbon number can be produced by means such as blending each shorter and longer fraction of carbon number. As such, C16.5 may be prepared by blending C16 and C17 or blending C14 and C17 and the like. Preferred distillates have a narrower "spread" carbon number in the blend. Alternatively, the desired distillate can be prepared by distillation on the olefinic branched concentrated stream immediately prior to the oxo reaction on the olefinic branched concentrated stream.

Of course, when distilling hydrocarbons herein, the boiling point of the desired methyl-branched hydrocarbon is generally lower than that of linear hydrocarbons of the same carbon number, of course it should be understood and appreciated for the purpose of implementation. Thus, preferred distillates (and e.g., distillates of apparently non-integer carbon number) boiling in the intermediate range between linear C15 and linear C16 paraffins are preferred in the methyl-branched isomers having a total of 16 carbon atoms which are preferred for the process of the invention Relatively rich

For the OXO-alcohol preparation process, if not uniquely very distinctly, the hydrocarbon feedstock is an adsorptive separation raffinate derived from a linear alkylbenzene preparation process or a conventional linear detergent alcohol process. That is, the present invention opens up all types of novel possibilities for combining the linear alkylbenzene preparation and / or conventional linear detergent alcohol processes with the OXO alcohol preparation in a manner not carried out so far. This makes the feed better utilized. In addition, when using the invention as taught herein, novel alkylbenzenes and OXO alcohols can be obtained. They can be prepared by themselves or can be prepared by substituting conventional linear alkylbenzenes and / or OXO alcohols by arranging plants suitably using the steps taught herein.

Once the modified primary OXO alcohol is produced, it can of course be converted to another useful derivative in the same plant or at a remote facility. For example, the process of the present invention comprises the steps of: (E) sulfate and neutralize the product of step (D); (F) alkoxylating the product of step (D); And (G) an additional step or series of steps selected from the step of alkoxylating, sulphating and neutralizing the product of step (D).

In addition, when surfactant derivatives of this kind are prepared, they can be easily incorporated into all types of cleaning compositions. For this purpose, when juxtaposed or remotely located in the same facility, the method of the invention may comprise (H) an additional step of mixing the product of the preceding step with one or more cleaning product aids to form a cleaning article. Can be.

As can be seen from the background, although various OXO alcohols are already well known (see, eg, Shell and Sasol methods), prior to the OXO step specifically identified herein There is no suggestion of applying a particular type of adsorptive separation. In addition, at least with regard to detergents, there is no suggestion so far of using the impractical stream portion available from linear alkylbenzene production. From the crude feed selection or from one or both of the specific adsorption steps, the composition of the resulting OXO alcohol is changed in relation to the shell and sasol method, which is particularly soluble (compressed granules, tablets) or high water, especially at low washing temperatures. It makes them very useful in the preparation of surfactants requiring hardness applications. All of these are achieved quite economically. Due to the change in the composition provided to the OXO alcohol, the present invention also includes modified primary OXO alcohols prepared by the process of the present invention.

The present invention also encompasses consumer product cleaning products prepared by the above-described methods comprising the specific OXO alcohol preparations presented herein, followed by mixing one or more cleaning product auxiliary components.

In other variations, the method herein comprises blending the product of step (B) or (C) with a conventional washable olefin, or the product of step (E), (F) or (G) before the OXO step (D). Blending with a conventional detergent.

Process of the Invention (The non-limiting method according to the invention further comprises the 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 an alkylation catalyst. Despite the presence of a number of arrangements that make it possible to produce both modified alkylbenzenes and modified primary OXO alcohols simultaneously or in alternative processing cycles. When prepared, the internal isomer selectivity of the alkylation catalyst is 0 to 40. Branching includes providing a means for feeding the product of steps (C) to (D) in parallel to the alkylation step or all of the above steps. Refer to the drawings for further examples.

More generally, the present invention also provides an effective amount of a cleaning surfactant selected from (a) alkyl sulfates, alkylpoly (alkoxy) sulfates, alkylpoly (alkoxylates), and mixtures thereof, wherein the surfactant is R in formula ROH = C9-C20 detergent alcohol, wherein R is a mixture of methyl side chains and certain straight chains, and the alcohol is at least one Fischer-Tropsch process step, or oligomerization or dimerization or skeletal isomerization step, or olefin and / or paraffin feed Further features comprising the product of the step (eg, via the adsorptive separation or alternative process, eg, wax hydroisomerization / hydrocracking, Flexicoking ^R , Fluidcoking ^R, etc.) and one or more OXO process step products Provided that in one or more stages prior to the OXO process stage, the proportion of methyl-branched olefins used as feed in the OXO process stage is increased. Incorporation of an RO- radical (not more than 1 mol, more preferably about 1 mol)] and (b) one or more auxiliary materials which contribute in part or in whole to the useful properties of the composition.

In addition, (a) an effective amount of a cleaning surfactant selected from alkyl sulfates, alkylpoly (alkoxy) sulfates, alkylpoly (alkoxylates), and mixtures thereof, wherein the surfactant is selected from R = C9-C20 detergent alcohol { Wherein R is a mixture of methyl side chains and a predetermined straight chain, and the alcohol further comprises the product of any of the above described modified primary OXO alcohol preparation processes. Included herein are detergents or cleaning compositions comprising one or more adjuvants that contribute in part or in whole to the useful properties of the composition.

Cleaning product aspect

Cleaning article embodiments of the present invention include laundry detergents, dishwashing detergents, hard surface detergents, and the like. In such embodiments, the content of surfactants derived from modified alkylbenzenesulfonates or modified primary OXO alcohols prepared by the present invention is about 0.1 to about 99.9%, typically about 1 to about 50%, and the composition The silver further comprises about 0.1 to about 99.9%, typically about 1 to about 50%, of a cleaning article aid such as a cosurfactant, builder, enzyme, bleach, bleach promoter, activator or catalyst and the like.

The present invention also provides

(a) about 0.1 to about 99.8%, more typically about 50% or less of a modified alkylbenzenesulfonate surfactant or a surfactant derived from a modified primary OXO alcohol as prepared according to the present invention and

(b) one or more cleaning article auxiliaries comprising about 0.00001%, more typically about 1% to 99%.

Auxiliaries can vary widely and can be used in a wide range of amounts. For example, the present invention allows the use of very small amounts of bleaching catalysts including macrocyclic types having manganese or similar transition metals useful for laundry and cleaning articles, as well as cleaning enzymes such as proteases, amylases, cellulases, lipases, and the like. Or, less commonly, in larger amounts.

Other cleaning article auxiliaries suitable for the present invention include bleaching agents, in particular bleach activators such as nonanoyloxybenzenesulfonate and / or tetraacetylethylenediamine and / or derivatives thereof or derivatives of phthaloylimidoperoxycaproic acid. Imido- or amido-substituted bleach activators (eg lactam type), more generally hydrophilic and / or hydrophobic bleach activators (especially acyl derivatives including derivatives of C6-C16 substituted oxybenzenesulfonates) Oxygen bleach forms including activated and catalyzed forms of a mixture of; Preformed peracids relating to or based on all of the aforementioned bleach activators; Insoluble types such as zeolites including zeolites A, P and so-called maximum aluminum P and phosphates, polyphosphates, all hydrates, water-soluble or water-insoluble silicates, 2,2'-oxydisuccinates, tartrate succinates Builders, including soluble types such as glycolate, NTA and many other ethercarboxylates or citrates; Chelating agents including EDTA, S, S'-EDTA, DTPA and phosphate; Auxiliary surfactant optical brighteners including water-soluble polymers, copolymers and terpolymers, antifouling polymers, known anionic, cationic, nonionic or zwitterionic types; Processing aids such as crisping agents and / or fillers, solvents, anti-repositioning agents, silicones / silica and other suss inhibitors, hydrophobic materials, flavoring or pre-fragrances, dyes, photobleaches, thickeners, simple salts and alkalis ( For example, sodium or potassium based hydroxides, carbonates, bicarbonates, sulfates and the like). When combined with the modified alkylbenzenesulfonate surfactants of the present invention, any of the anhydrous, hydrous, aqueous or solvent containing cleaning articles can be in granules, solutions, tablets, powders, flakes, gels, extracts, pouches or encapsulated forms. It can be obtained easily. Accordingly, the present invention also includes a number of cleaning articles that can be made or formed by all of the above methods. They can be used in discrete dose form manually or mechanically or continuously added to any suitable cleaning article or conveying device.

Concrete cleaning supplies

The documents cited herein are incorporated by reference. Surfactant compositions prepared by the process of the present invention include powders, granules, gels, pastes, tablets, pouches, bars, types contained in double-compartment containers, spray or foamed detergents, and other homogeneous or multiphase consumer product types. It can be used in a wide range of consumable cleaning article compositions. They may be used or applied manually and / or may be applied by means of a single dose or freely varying capacity or automatic dispensing device, useful for appliances such as washers or dishwashers, or for body washing in public facilities, It can be used for public cleaning items including bottle cleaning, surgical instrument cleaning or electronic component cleaning. They have a wide range of pH, for example from about 2 to about 12 or more, and from very high alkalinity, such as in the case of liquid hard cleaners, for applications such as drainage prevention, where dozens of grams of NaOH can be present per 100 g of formulation. It may have a wide range of alkalinity, such as from 1 to 10 g of NaOH and medium or low alkalinity, as in acidic hard-surface cleaners, to which the alkalinity falls towards the acid. Both high- and low-foaming detergent types are included.

Consumable cleaning article compositions are described in "Surfactant Science Series", Marcel Dekker, New York, Volumes 1-67f. In particular, liquid compositions are described in Volume 67, "Liquid Detergents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9. More typical formulations, especially types of granules, are incorporated herein by reference, "Detergent Manufacture including Zeolite Builders and Other New Materials", Ed. M. Sittig, Noyes Data Corporation, 1979. See also Kirk Othmer's Encyclopedia of Chemical Technology.

Consumable cleaning article compositions of the present invention include, but are not limited to:

Hard Liquid Detergent (LDL) : These compositions include magnesium ions that enhance the surface activity (eg, WO 97/00930 A, GB 2,292,562 A, US Pat. No. 5,376,310, US Pat. No. 5,269,974, US Pat. 5,230,823, U.S. Patent 4,923,635, U.S. Patent 4,681,704, U.S. Patent 4,316,824, U.S. Patent 4,133,779) and / or foaming accelerators such as organic diamines and / or various foam stabilizers and / or amine oxides ( See, for example, US Pat. No. 4,133,779) and / or LDL compositions comprising an enzyme type skin feel modifier and / or antibacterial agent, including surfactants, emollients and / or proteases, see Surfactant Science. Series, Vol. 67, pages 240-248, list more extensive patent documents.

Heavy Liquid Detergent (HDL) : These compositions are so-called "structured" or multiphase types (e.g., U.S. Patent 4,452,717, U.S. Patent 4,526,709, U.S. Patent 4,530,780, U.S. Patent 4,618,446, U.S. Patent 4,793,943, U.S.A. Patents 4,659,497, U.S. Patent 4,871,467, U.S. Patent 4,891,147, U.S. Patent 5,006,273, U.S. Patent 5,021,195, U.S. Patent 5,147,576, U.S. Patent 5,160,655) and "non-structured" or isotropic liquid types Both of which are generally aqueous or non-aqueous (e.g. EP 738,778 A, WO 97/00937 A, WO 97/00936 A, EP 752,466 A, DE 19623623 A, WO 96/10073 A, WO 96/10072 A, US Patent 4,646,393, US Patent 4,648,983, US Patent 4,655,954, US Patent 4,661,280, EP 225,654, US Patent 4,690,771, U.S. Patent 4,744,916, U.S. Patent 4,753,750, U.S. Patent 4,950,4 24, US Pat. No. 5,004,556, US Pat. No. 5,102,574, WO 94/23009) and bleach (e.g., US Pat. No. 4,470,919, US Pat. No. 5,250,212, EP No. 564,250, US Pat. 5,264,143, U.S. Patent 5,275,753, US 5,288,746, WO 94/11483, EP 598,170, EP 598,973, EP 619,368, U.S. Patent 5,431,848, U.S. Patent 5,445,756) And / or enzymes (eg, US Pat. No. 3,944,470, US Pat. No. 4,111,855, US Pat. No. 4,261,868, US Pat. No. 4,287,082, US Pat. No. 4,305,837, US Pat. No. 4,404,115, US Pat. No. 4,462,922, U.S. Patent 4,529,525, U.S. Patent 4,537,706, U.S. Patent 4,537,707, U.S. Patent 4,670,179, U.S. Patent 4,842,758, U.S. Patent 4,900,475, U.S. Patent 4,908,150, U.S. Patent 5,082,585, U.S. Patent No. 5,156,773, WO 92/19709, EP 583,534, EP 583,535, EP 583,536, WO 94/04542, U.S. Patent 5,269,960, EP 633,311, U.S. Patent 5,422,030, U.S. Patent 5,431,842, U.S. Patent 5,442,100) And / or may not contain both enzymes. Other patent literature on heavy liquid detergents is described in Surfactant Science Series, Vol. 67, pages 309-324, listed or listed.

Heavy Granular Detergent (HDG) : These compositions include both so-called "compact" or aggregated or otherwise non-spray dried types as well as so-called "fluffy" or spray dried types. Both phosphorylated and non-phosphorylated types are included. Such detergents may include types based on more conventional anionic surfactants, or are commonly referred to as "high-boiling" in which nonionic surfactants are retained in or on an adsorbent such as zeolites or other porous inorganic salts. Warm surfactant "type. As for the production method of HDG, for example, EP 753,571 A, WO 96/38531 A, US Patent 5,576,285, US Patent 5,573,697, WO 96/34082 A, US Patent 5,569,645 No. EP, 739,977 A, U.S. Patent 5,565,422, EP 737,739 A, WO 96/27655 A, U.S. Patent 5,554,587, WO 96/25482 A, WO 96/23048 A, WO 96/22352 A, EP 709,449 A, WO 96/09370 A, US Pat. No. 5,496,487, US Pat. No. 5,489,392 and EP 694,608 A.

"Softeners" (STW) : These compositions are prepared in various granular or liquid phases (e.g. EP 753,569 A, US Patent 4,140,641, US Patent 4,639,321, US Patent 4,751,008, EP 315,126, US Patent). 4,844,824, U.S. Patent 4,873,001, U.S. Patent 4,911,852, U.S. Patent 5,017,296, EP 422,787), including softening-through-the wash products, generally organic (Eg, quaternary) or inorganic (eg, clay) softeners.

Hard Surface Cleaners (HSC) : These compositions include universal cleaners such as cream cleaners and liquid universal cleaners, universal spray cleaners including glass and tile cleaners and bleach spray cleaners, and mold-removal types, bleach-containing types, antimicrobial types, Bathroom cleaners, including acidic, neutral and basic types (see, for example, EP 743,280 A, EP 743,279 A). Acidic cleaners include those described in WO 96/34938 A.

Bar Soaps and / or Laundry Bars (BS & HW) : These compositions are for body cleansing comprising both synthetic detergents and soap-based types and types comprising softeners (see US Pat. No. 5,500,137 or WO 96/01889 A). Bars as well as so-called laundry bars (e.g. WO 96/35772 A), these compositions adsorb onto a porous support and / or castings of conventional soap making techniques such as flooding and / or casting And those made by less conventional techniques such as and the like. Other bar soaps are also included (eg, BR 9502668, WO 96/04361 A, WO 96/04360 A, US Pat. No. 5,540,852). Other handwash detergents include detergents as described in GB 2,292,155 A and WO 96/01306 A.

Shampoos and conditioners (S & C) : (see, eg, WO 96/37594 A, WO 96/17917 A, WO 96/17590 A, WO 96/17591 A). Such compositions generally include both shampoo-only types and so-called "two-in-one" or "conditioner containing" types.

Liquid Soaps (LS) : These compositions include both so-called "antibacterial" types as well as those with or without skin conditioners and are suitable for use by other means such as pump dispensers and commonly used wall-mounting devices. Includes suitable types.

Specific Use Cleaning Agents (SPCs) : Household dry cleaning systems (e.g. WO 96/30583 A, WO 96/30472 A, WO 96/30471 A, US Pat. No. 5,547,476, WO 96). / 37652 A), laundry bleach pretreatment products (see EP 751,210 A), textile protective pretreatment products (see EP 752,469 A), liquid detergent types for high-quality fabrics, in particular foam High type, dishwashing rinse aid, liquid bleach comprising both chlorine and oxygen bleach types, and disinfectants, mouthwashes, denture cleaners (eg WO 96/19563 A, WO 96/19562 A). Car or carpet cleaners or shampoos (for example EP 751,213 A, WO 96/15308 A), hair rinses, shower gels, foam baths and body protective cleaners (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 bleach aids and special foamed cleaners (eg EP 753,560 A, EP 753,559 A). No. EP 753,558 A, EP 753,557 A, EP 753,556 A) and anti-pigmentation treatment by sunlight (WO 96/03486 A, WO 96/03481 A, WO 96/03369 A) Cleaning aids, such as “stain-adhering” or other types of pre-treatment, are hereby incorporated by reference.

Detergents containing a persistent perfume (see, eg, US Pat. No. 5,500,154, WO 96/02490) are becoming increasingly popular.

Process integration

The process of the present invention can be integrated with the latest LAB manufacturing processes in any conventional manner. For example, conventional assembly plants can be switched to produce modified alkylbenzenes and / or modified primary OXO alcohols in complete form. Alternatively, the modified alkylbenzenes and / or modified primarys of the present invention, depending on the volume of the preferred or available feedstock, eg, effluent from the LAB process, or based on nearby feedstock sources from the petrochemical industry. The plant for producing OXO alcohol can be assembled into an existing LAB plant as an add-on or supplement or as a stand-alone unit. Both batch and continuous operation of the method of the invention are contemplated.

In an adjunct mode, the present invention comprises the steps of producing the modified alkylbenzenes or alkyltoluenes and / or modified primary OXO alcohols from vinylidene olefins and vinylidene olefins using the steps described above. The modified alkylbenzene or alkyltoluene and / or modified primary OXO alcohol is in a ratio of about 1: 100 to 100: 1, more typically about 1:10 to about 10: 1, for example about 1: 5. To conventional linear alkylbenzenes such as C11.8 average alkylbenzenes or any alkylbenzene prepared by the DETAL ^R process. The blend is then sulfonated, neutralized and incorporated into a consumable cleaning article composition. The parallel process step or alternative process step produces a modified primary OXO alcohol.

The present invention should not be considered as limited to the details illustrated in the specification, including the embodiments illustrated below. Most generally, the present invention should be considered to include all consumable cleaning article compositions including the hydrophobicity of the surfactant, including all types of surfactants modified by the methods using the essential teachings of the present invention. In particular, it is contemplated that the teachings of the present invention relating to the delinearization process may also be applicable to, for example, preparing modified alkyl sulfates and other surfactants.

Example 1

Branched hydrocarbon-containing feeds supplied from jets / diesel; Separation on SAPO-11; Dehydrogenation; Alkylation on H-mordenite; Sulfonation using sulfur trioxide / air; And modified alkylbenzenesulfonates prepared by neutralization

Suitable feeds are obtained in the form of jet / diesel distillate distillates from kerosene. The feed contains paraffinic branched hydrocarbons and linear hydrocarbons, where the chain length of the linear hydrocarbons is suitable for the production of LABs, the branched hydrocarbons being methyl branched paraffins with cyclic hydrocarbons, aromatic hydrocarbons and other impurities. About 10% or more. The stream is continuously transferred to two adsorptive separation apparatus connected as shown in FIGS. 8 and 1, where the device AC1 of FIG. 8 is loaded with 5 μC Ca zeolite used in a typical linear alkylbenzene process and detailed The device AC2 of FIG. 8 is loaded with silicoaluminophosphate SAPO-11. Devices AC1 and AC2, together with connected rotary valve devices, raffinate columns and effluent columns (RC and EC) and condensers (represented by horizontal tanks not specified in FIG. 8) and other suggested means, connected in a unique way, are generally The configuration is in accordance with a device approved and commercially available from UOP Corporation (MOLEX ^R device). The raffinate from the Ca zeolite adsorption device AC1 is discharged and the adsorbate (extract) is continuously delivered to a second adsorptive separation device AC2 containing SAPO-11. The branched hydrocarbon-rich stream obtained from the apparatus AC2 as adsorbate was dehydrogenated to standard commercial LAB process charged with standard LAB dehydrogenation catalyst (DeH 5 _R or DeH 72-carbon distillate or similar catalyst) provided by UOP Corporation. Delivered to the device (source: UOP Corp .; PACOL ^R process). After dehydrogenation under conventional LAB-manufacturing process conditions, the hydrocarbons are continuously transferred to a conventional alkylation apparatus, except that the hydrocarbons are charged with H-mordenite (ZEOCAT ^R FM 8/25 H), wherein alkylation is about The process proceeds continuously with a discharge of at least about 90% of the end point at a temperature of 200 ° C., ie at least about 90% of the incoming hydrocarbons (olefins) are converted. This produces a modified alkylbenzene. In any variation, the above procedure is repeated except that the discharge is at least about 80% conversion (based on olefins) to the desired modified alkylbenzene. The recycle of paraffin is obtained by distillation at the end of the alkylation apparatus, and the recycle is passed back to the dehydrogenator. The process for this time includes the steps and stream in FIG. The modified alkylbenzenes can be further purified by further conventional distillation (this distillation step is not shown in FIG. 1). The distilled modified alkylbenzene mixture is sulfonated batchwise or continuously, optionally in a remote plant, with sulfur trioxide as the sulfonating agent. Details of sulfonation using suitable air / sulfur trioxide mixtures are provided in US Pat. No. 3,427,342 to Chemithon. The modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to obtain a modified alkylbenzene sulfonate, sodium salt mixture.

Example 2

Reforming via hydrocarbon feed fed from MOLEX ^R effluent, separation on SAPO-11, dehydrogenation using standard UOP method, alkylation on H-mordenite, sulfonation and neutralization using sulfur trioxide / air Alkylbenzenesulfonates

Suitable feedstocks are obtained in the form of effluents or raffinates from LAB plants, in particular from MOLEX ^R process equipment of such plants. The raffinate contains a high proportion of branched paraffinic hydrocarbons with undesired cyclic hydrocarbons, aromatic hydrocarbons and other impurities. The raffinate is continuously transferred to a conventionally configured adsorptive separation device comprising a charge of SAPO-11, for example after the MOLEX ^R device. The device operates under similar conditions generally as the MOLEX ^R device used in the linear alkylbenzene preparation and is similar to the device AC2 described in Example 1. Drain the raffinate or effluent from the SAPO-11 adsorber, and adsorbate or extract, which now conforms to the definition of the branched hydrocarbon-rich stream, of the standard LAB dehydrogenation catalyst provided by UOP Corporation (eg DeH). Continuous transfer to a standard commercial LAB process dehydrogenation unit (source: UOP Corp .; PACOL ^R process) filled with 7 ^R ). After dehydrogenation under conventional LAB-manufacturing process conditions, the hydrocarbons are continuously transferred to a conventional alkylation apparatus, except that the hydrocarbons are charged with H-mordenite (ZEOCAT ^R FM 8/25 H), wherein alkylation is about The process proceeds continuously while discharging at a temperature of 200 ° C. to achieve at least about 90% conversion of the alkylating agent. The modified alkylbenzene mixture is purified by conventional distillation and the branched paraffins are recycled to the dehydrogenation unit. The steps in the process for this time point are in accordance with FIG. 4.

The distilled modified alkylbenzene mixtures prepared in the process for this point are sulfonated batchwise or continuously, optionally in remote plants, with sulfur trioxide as the sulfonating agent. Details of sulfonation using suitable air / sulfur trioxide mixtures are provided in US Pat. No. 3,427,342 to Chemithon. The modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to obtain a modified alkylbenzene sulfonate, sodium salt mixture.

Example 3

Hydrocarbon feed fed from MOLEX ^R effluent, separation on pyrolyzed poly (vinylidene chloride), dehydrogenation using standard UOP method, alkylation on H-ZSM-12, sulfonation and neutralization using sulfur trioxide / air Modified Alkylbenzenesulfonates Prepared Via

Suitable feedstocks are obtained in the form of effluents or raffinates from LAB plants, in particular MOLEX ^R process equipment of such plants. The raffinate contains branched paraffinic hydrocarbons with cyclic hydrocarbons, aromatic hydrocarbons and other unwanted impurities. The raffinate is conventional in construction (e.g. MOLEX ^R type), but is not typically introduced into LAB plant design, and then contains a charge of pyrolyzed poly (vinylidene chloride) and a sieve diameter of more than 5 mm 3 and the Dutch patent application Continuously transferred to an adsorptive separation apparatus called "SARAN ^R apparatus" made according to NL 7111508 (published October 25, 1971). The "SARAN device" operates under similar conditions as the MOLEX ^R device. The raffinate from the "SARAN unit" is discharged and the adsorbate is packed with a standard commercial LAB process dehydrogenation unit charged with a standard LAB dehydrogenation catalyst such as DeH 7 ^R provided by UOP Corporation (Source: UOP Corp .; PACOL ^R Process). After dehydrogenation under conventional LAB-manufacturing process conditions, the hydrocarbons are continuously transferred to a conventional alkylation apparatus, except that the hydrocarbons are charged with H-ZSM 12, wherein alkylation is at least about 90% at a temperature of about 200 ° C. The process proceeds continuously while discharging to reach conversion of the incoming hydrocarbons. The modified alkylbenzene mixture prepared in the preceding step is distilled and sulfonated batchwise or continuously with sulfur trioxide as the sulfonating agent. Details of sulfonation using suitable air / sulfur trioxide mixtures are provided in US Pat. No. 3,427,342 to Chemithon. The modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to obtain a modified alkylbenzene sulfonate, sodium salt mixture.

Example 4

Modified alkylbenzene prepared via hydrocarbon feed from urea inclusion, separation on SAPO-11, dehydrogenation with Pt catalyst, alkylation on acidic zeolite beta, sulfonation with sulfur trioxide / air and neutralization Sulfonate

Suitable feedstocks are obtained from kerosene by urea inclusions where more commercially available linear hydrocarbons are used to remove concentrated distillates (see US Pat. No. 3,506,569). Low-grade branched effluent from the urea inclusion step is a suitable hydrocarbon feed for the process of the present invention. If present, the activator solvent, such as methanol, is removed and transferred continuously to the adsorptive separation apparatus constructed in a conventional manner, for example, after the method of a MOLEX ^R process apparatus which comprises a charge of SAPO-11 but is charged differently. Let's do it. The SAPO-11 unit operates under conditions similar to standard MOLEX ^R process units. The raffinate from the SAPO-11 unit is discharged and continuously transferred to a standard industrial LAB process dehydrogenation unit (source: UOP Corp .; PACOL ^R process) filled with the universal platinum dehydrogenation catalyst. After dehydrogenation under conventional LAB-manufacturing process conditions, the hydrocarbon is continuously transferred to a conventional alkylation apparatus except for Zeocat PB / H ^R charge, wherein alkylation is at least about 90% at a temperature of about 200 ° C. The process proceeds continuously while discharging to reach conversion of the incoming hydrocarbons. The modified alkylbenzene mixture prepared in the preceding step is sulfonated batchwise or continuously using sulfur trioxide as the sulfonating agent. Details of sulfonation using suitable air / sulfur trioxide mixtures are provided in US Pat. No. 3,427,342 to Chemithon. The modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to obtain a modified alkylbenzene sulfonate, sodium salt mixture.

Example 5

Hydrocarbon feed from kerosene distillate from high paraffinic petroleum source, separation on grafted non-acidic zeolite, dehydrogenation using DeH 9 ^R catalyst, alkylation on H- mordenite, chlorosulfonic acid Modified alkylbenzenesulfonates prepared via sulfonation and neutralization

Jet / kerosene distillates are obtained from low viscosity crude oils such as via Brent. This is, for example, after the manner of the MOLEX ^R process apparatus, continuously transferred to a differently charged but typically configured adsorptive separation apparatus, including a charge of grafted zeolites prepared according to US Pat. No. 5,326,928. The device is typically operated under similar conditions as a charged MOLEX ^R device. Continuously with a standard commercial LAB process dehydrogenation unit (source: UOP Corp .; PACOL ^R process) discharged raffinate from this unit and packed with adsorbate with standard LAB dehydrogenation catalyst DeH 9 ^R exclusive to UOP Corporation. Transfer it. After dehydrogenation under conventional LAB-manufacturing process conditions, the hydrocarbons are continuously transferred to a conventional alkylation apparatus, except that the hydrocarbons are charged with H-mordenite (ZEOCAT ^R FM 8/25 H), wherein alkylation is about The process proceeds continuously with the exhaust reaching a conversion of at least about 90% of the incoming hydrocarbons at a temperature of 200 ° C. The modified alkylbenzene mixture prepared in the preceding step is sulfonated batchwise or continuously using sulfur trioxide as the sulfonating agent. Details of sulfonation using suitable air / sulfur trioxide mixtures are provided in US Pat. No. 3,427,342 to Chemithon. The modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to obtain a modified alkylbenzene sulfonate, sodium salt mixture.

Example 6

Cleaning Supplies Composition

10% by weight of the modified alkylbenzenesulfonate sodium salt product of any of the methods exemplified above is combined with 90% by weight of the aggregated compressed laundry detergent granules.

Example 7

Cleaning Supplies Composition

In this example, the following abbreviations are used for modified alkylbenzenesulfonates (MAS) in the sodium salt form or potassium salt form prepared according to any of the preceding methods:

The following abbreviations are used for cleaning article aids:

Cxy amine oxide: Alkyldimethylamine N-oxide RN (O) Me2 of the specified chain length Cxy, where the average total carbon range of the non-methyl alkyl residue R is 10 + x to 10 + y

Amylase: active 60 KNU / g starch enzyme from NOVO Industries A / S, trade name; Termamyl 60T. Or amylases selected from Fungamyl ^R , Duramyl ^R , BAN ^R and α-amylase enzymes described in co-pending patents by WO95 / 26397 and Novo Nordisk PCT / DK96 / 00056

APA: C8-C10 Amido Propyl Dimethyl Amine

Cxy betaine: Alkyldimethyl betaine with an average total carbon range of 10 + x to 10 + y of alkyl moieties

Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution of 400 to 1200 μm

Borax: Na tetraborate decahydrate

BPP: Butoxy-propyl-propanol

Brightener 1: Disodium 4,4'-bis (2-sulphostyryl) biphenyl

Brightener 2: Disodium 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilben-2,2'-disulfonate

CaCl ₂ : calcium chloride

Carbonate: Anhydrous Na ₂ CO ₃ , 200 μm to 900 μm

Cellulase: Fibrinolytic enzyme, 1000 CEVU / g manufactured by NOVO, trade name; Carezyme ^R

Citrate: Trisodium Citrate Dihydrate, 86.4%, 425 μm to 850 μm

Citric Acid: Citric Acid Anhydrous

CMC: Sodium Carboxymethyl Cellulose

CxyAS: Alkyl sulfates, Na salts or other salts, if specified, with an average total carbon range of 10 + x to 10 + y alkyl moieties.

CxyEz: Commercial linear or branched alcohol ethoxylates with an average total carbon range of alkyl moieties of 10 + x to 10 + y and z moles of ethylene oxide (not including heavy chain methyl branches)

CxyEzS: Alkyl ethoxylate sulfate, Na salt (or other salt, if specified) with an average total carbon range of 10 + x to 10 + y alkyl moiety and zmol ethylene oxide

Diamines: alkyl diamines such as 1,3-propanediamine, Dytek EP, Dytek A from Dupont, and dimethyl aminopropyl amine, 1,6-hexanediamine, 1,3-propanediamine, 2-methyl Alkyl diamine selected from 1,5-pentanediamine, 1,3-pentanediamine, 1-methyl-diaminopropane, 1,3-cyclohexanediamine and 1,2-cyclohexanediamine

Dimethicone: Blend of SE-76 dimethicone rubber (G.E Silicones Div.) / Dimethicone fluid with a viscosity of 350 cS at a weight ratio of 40 (rubber) / 60 (fluid)

DTPA: diethylene triamine pentaacetic acid

DTPMP: diethylene triamine penta (methylene phosphonate) manufactured by Monsanto, trade name: Dequest 2060

Endolase: endoglucanase, active 3000 CEVU / g manufactured by NOVO

EtOH: Ethanol

Fatty acid (C12 / 18): C12-C18 fatty acid

Fatty acid (C12 / 14): C12-C14 fatty acid

Fatty acid (C14 / 18): C14-C18 fatty acid

Fatty Acids (RPS): Rapeseed Fatty Acid

Fatty acid (TPK): fatty acid topping palm

Formate: Formate (Sodium)

HEDP: 1,1-hydroxyethane diphosphonic acid

Flexible materials: selected from toluene sulfonic acid, naphthalene sulfonic acid, cumene sulfonic acid, sodium, potassium, magnesium, calcium, ammonium or water-soluble substituted ammonium salts of xylene sulfonic acid

Isofol 12: X16 (Average) Gourbet Alcohol (Condea)

Isofol 16: C16 (Average) Gourbet Alcohol (Condea)

LAS: linear alkylbenzene sulfonates such as C11.8, Na or K salts

Lipase: Lipolytic enzyme, 100 kLU / g from NOVO, trade name: Lipolase ^R. Or Amino-P; M1 Lipase ^R ; Lipomax ^R ; D96L-lipase enzyme variants of natural lipases derived from Humicola lanuginosa and from Humicola ranuginosa strain DSM 4106 as described in US 08 / 341,826.

LMFAA: C12-C14 Alkyl N-methyl Glucamide

MA / AA: 1: 4 copolymer of maleic acid / acrylic acid, Na salt, average molecular weight 70,000

MBAxEy: heavy chain branched primary alkyl ethoxylate (average total carbon number = x, average EO = y)

MBAxEyS: heavy chain branched or modified primary alkyl ethoxylate sulfate, Na salt (average total carbon number = x, average EO = y) according to the invention (see Example 9)

MBAyS: heavy chain branched primary alkyl sulfate, Na salt (average total carbon number = y)

MEA: monoethanolamine

Cxy MES: Alkyl methyl ester sulfonates, Na salts with an average total carbon number ranging from 10 + x to 10 + y

MgCl ₂ : Magnesium Chloride

MnCAT: macrocyclic manganese bleach catalyst as described in EP 544,440 A, or preferably [Mn (Bcylclam) Cl ₂ ], where Bcyclam is 5,12-dimethyl-1,5,8,12- Tetraaza-bicyclo [6.6.2] hexadecane or similar crosslinked tetra-aza macrocycles)

NaDCC: Sodium Dichloroisocyanurate

NaOH: Sodium Hydroxide

Cxy NaPS: paraffin sulfonate, Na salt with an average total carbon number ranging from 10 + x to 10 + y alkyl moieties

NaSKS-6: Crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅

NaTS: Sodium Toluene Sulfonate

NOBS: nonanoyloxybenzene sulfonate, sodium salt

LOBS: C12 oxybenzenesulfonate, sodium salt

PAA: Polyacrylic Acid (Molecular Weight = 4500)

PAE: Ethoxylated Tetraethylene Pentaamine

PAEC: Methyl Quaternary Ethoxylated Dihexylene Triamine

PB1: anhydrous sodium perborate bleach of formula NaBO ₂ H ₂ O ₂

PEG: polyethylene glycol (molecular weight = 4600)

Percarbonate: Sodium percarbonate of formula 2Na ₂ CO ₃ .3H ₂ O ₂

PG: Propanediol

Photobleach: sulfonated zinc phthalocyanine encapsulated in dextrin soluble polymer

PIE: Water-soluble ethoxylated polyethyleneimine

Protease: proteolytic enzyme, 4KNPU / g from NOVO, trade name Savinase ^R. Or proteases selected from Maxatase ^R , Maxacal ^R , Maxapem 15 ^R , subtilisin BPN and BPN ′; Protease B; Protease A; Protease D; Primase ^R ; Durazym ^R ; Opticlean ^R ; Optimase ^R ; And Alcalase ^R

QAS: R ₂ N ⁺ (CH ₃ ) _x ((C ₂ H ₄ O) _y H) _z (wherein R ₂ is C8-C18, x + z is 3, x is 0-3, z is 0 to 3, y is 1 to 15)

Cxy SAS: secondary alkyl sulfates, Na salts with an average total carbon number ranging from 10 + x to 10 + y alkyl moieties

Silicate: Sodium Silicate, Amorphous (SiO ₂ : Na ₂ O = 2.0)

Silicone antifoams: siloxane-oxyalkylene copolymers as polydimethylsiloxane foam inhibitors + dispersants; Foam inhibitor: dispersant = 10: 1 to 100: 1; Or a combination of fumed silica and high viscosity polydimethylsiloxane (optionally chemically modified)

Solvent: Non-aqueous solvent such as hexylene glycol, also propylene glycol

SRP 1: sulfobenzoyl end capped ester comprising oxyethylene oxy and terephthaloyl backbone

SRP 2: sulfonated ethoxylated terephthalate polymer

SRP 3: methyl capped ethoxylated terephthalate polymer

STPP: Sodium Tripolyphosphate Anhydrous

Sulfate: Anhydrous Sodium Sulfate

TAED: tetraacetylethylenediamine

TFA: C16-C18 Alkyl N-methyl Glucamide

Zeolite A: Hydrated sodium _{aluminosilicate, Na 12 (AlO 2 SiO 2} ) 12 · 27H 2 O; 0.1 to 10 μm

Zeolite MAP: Zeolite (Max Aluminum P) Detergent Grade (Crosfield)

Typical ingredients, often referred to as "trace ingredients," may include perfumes, dyes, pH adjusters, and the like.

The examples are intended to illustrate the invention and are not intended to limit or otherwise define the scope thereof. All parts, percentages and ratios used are expressed in weight percent unless otherwise noted. The following laundry detergent compositions A to F are prepared according to the invention:

A B C D E F MAS 22 16.5 11 1-5.5 10-25 5-35 Any combination of C45ASC45E1SLASC26 SASC47 NaPSC48 MESMBAS16.5SMBA15.5E2S 0 1-5.5 11 16.5 0-5 0-10 QAS 0-2 0-2 0-2 0-2 0-4 0 C23E6.5 or C45E7 1.5 1.5 1.5 1.5 0-4 0-4 Zeolite A 27.8 0 27.8 27.8 20-30 0 Zeolite MAP 0 27.8 0 0 0 0 STPP 0 0 0 0 0 5-65 PAA 2.3 2.3 2.3 2.3 0-5 0-5 lead carbonate 27.3 27.3 27.3 27.3 20-30 0-30 Silicate 0.6 0.6 0.6 0.6 0-2 0-6 PB1 1.0 1.0 0-10 0-10 0-10 0-20 NOBS 0-1 0-1 0-1 0.1 0.5-3 0-5 LOBS 0 0 0-3 0 0 0 TAED 0 0 0 2 0 0-5 MnCAT 0 0 0 0 2 ppm 0-1 Protease 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 0-1 Cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.5 0-1 Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-1 0-1 SRP 1 or SRP 2 0.4 0.4 0.4 0.4 0-1 0-5 Brightener 1 or 2 0.2 0.2 0.2 0.2 0-0.3 0-5 PEG 1.6 1.6 1.6 1.6 0-2 0-3 Silicone antifoam 0.42 0.42 0.42 0.42 0-0.5 0-1 Sulfate, water and trace ingredients To reach as early as 100 to 100% to 100% to 100% to 100% to 100% Density (g / L) 400-700 600-700 600-700 600-700 600-700 450-750

Example 8

Cleaning Supplies Composition

The following liquid laundry detergent compositions A to E are prepared according to the invention. The abbreviation is as used in the above-mentioned embodiment.

A B C D E MAS 1-7 7-12 12-17 17-22 1-35 C25E1.8-2.5SMBA15.5E1.8SMBA15.5SC25AS (Linear to Higher 2-Alkyl) C47 NaPSC26 Any combination of SASLASC26 MES 15-21 10-15 5-10 0-5 0-25 LMFAA 0-3.5 0-3.5 0-3.5 0-3.5 0-8 C23E9 or C23E6.5 0-2 0-2 0-2 0-2 0-8 APA 0-0.5 0-0.5 0-0.5 0-0.5 0-2 Citric acid 5 5 5 5 0-8 Fatty acid (TPK or C12 / 14) 2 2 2 2 0-14 EtOH 4 4 4 4 0-8 PG 6 6 6 6 0-10 MEA One One One One 0-3 NaOH 3 3 3 3 0-7 Flexural material or NaTS 2.3 2.3 2.3 2.3 0-4 Formate 0.1 0.1 0.1 0.1 0-1 borax 2.5 2.5 2.5 2.5 0-5 Protease 0.9 0.9 0.9 0.9 0-1.3 Lipase 0.06 0.06 0.06 0.06 0-0.3 Amylase 0.15 0.15 0.15 0.15 0-0.4 Cellulase 0.05 0.05 0.05 0.05 0-0.2 PAE 0-0.6 0-0.6 0-0.6 0-0.6 0-2.5 PIE 1.2 1.2 1.2 1.2 0-2.5 PAEC 0-0.4 0-0.4 0-0.4 0-0.4 0-2 SRP 2 0.2 0.2 0.2 0.2 0-0.5 Brightener 1 or 2 0.15 0.15 0.15 0.15 0-0.5 Silicone antifoam 0.12 0.12 0.12 0.12 0-0.3 Fumed silica 0.0015 0.0015 0.0015 0.0015 0-0.003 Spices 0.3 0.3 0.3 0.3 0-0.6 dyes 0.0013 0.0013 0.0013 0.0013 0-0.003 Water / trace element Residual amount Residual amount Residual amount Residual amount Residual amount Product pH (10% in demineralized water) 7.7 7.7 7.7 7.7 6-9.5

Example 9

In this example, a branched hydrocarbon-rich hydrocarbon stream is prepared, dehydrogenated and hydroformylated to produce modified primary OXO alcohols, ethoxylated and sulfated.

Suitable crude hydrocarbon feeds are purchased in the form of jet / diesel or kerosene distillates. These feeds are low in sulfur, nitrogen and aromatic hydrocarbons (to the extent that they are known to have significant side effects on the lifetime of the MOLEX ^R and OLEX ^R adsorption beds), linear hydrocarbons have a chain length suitable for detergent preparation, and Hydrocarbons, together with cyclic hydrocarbons, aromatic hydrocarbons and other impurities, contain paraffinic branched hydrocarbons and linear hydrocarbons comprising at least about 10% methyl branched paraffins.

The crude hydrocarbon feed is distilled off to give a two-carbon distillate at about C14-C15. This forms a hydrocarbon feed suitable for the rest of the process. See stream 1 of FIG. 10.

The distilled hydrocarbon feed was loaded with two adsorptive separation units (wherein device SOR 4/5 was loaded with 5 kPa zeolite as used in the conventional linear alkyl benzene recipe, as shown in FIG. 10, and device SOR 5 / 7 is continuously loaded with silicoaluminophosphate SAPO-11). The overall structure of the devices SOR 4/5 and SOR 5/7 and the accessory devices not shown in FIG. 10 is consistent with the devices available through UOP Corporation and commercially available devices (MOLEX ^R devices). Desorption system and accompanying distillation and recovery column are not shown. Withdrawal of the linear hydrocarbon-rich stream (stream 6 of FIG. 10, enriched with linear hydrocarbons) from the Ca zeolite MOLEX ^R apparatus SOR 4/5 and the intermediate branched hydrocarbon-rich stream (concentrated with branched hydrocarbons) Stream 2) is continuously sent to a second adsorptive separation apparatus containing SAPO-11. Branched hydrocarbon-enriched streams (stream 3 of Figure 10, more branched hydrocarbons) as adsorbates or extracts taken from apparatus SOR 5/7 are subjected to standard dehydrogenation catalysts (DeH 5 ^R or DeH 7 with exclusive rights to UOP Corporation). in a standard commercial LAB process dehydrogenation unit (10 filled with the ^R or the like) DEH) (purchased circle: transports by UOP Corp., ^R PACOL process). After partial dehydrogenation (up to about 20%) under conventional LAB olefin feed preparation process conditions, the branched hydrocarbon-enriched olefin / paraffin mixture (stream 4 in FIG. 10) was approved from UOP Corporation by DEFINE ^R and PEP ^R. Continuously transferred to the process equipment. These devices hydrogenate diolefins to monoolefins and reduce the content of aromatic impurities, respectively. The resulting purified olefin / paraffin stream (54 in FIG. 10) is transferred from the UOP to the approved OLEX ^R process equipment, filled with olefin separation adsorbate proprietary to UOP Corporation. After separating olefins from unreacted paraffin (the latter is recycled as stream 8 in FIG. 10), branched hydrocarbon-enriched olefinic hydrocarbons (stream 55 in FIG. 10) are operated at a 2-2.5: 1 H ₂ : CO ratio. And continuously transferred to an OXO reaction apparatus filled with a cobalt organophosphine complex using a pressure of about 60 to 90 atm and a temperature of about 170 to about 210 ° C. OXO proceeds to exit continuously when the selectivity to the modified primary OXO alcohol reaches about 90% or more to react almost all olefins in the inlet stream. This produces a modified primary OXO alcohol according to the present invention. It also decreases in small amounts to form paraffins. The paraffins can be separated by distillation and then recycled to the dehydrogenator. The process at this point includes the steps and stream of FIG. The modified primary OXO alcohol (stream 57 in FIG. 10) is ethoxylated with an average 1 mol of ethylene oxide content. Alternatively, ethoxylation, propoxylation, etc. using different amounts of alkylene oxide can be carried out to produce the desired alkoxylates. This is carried out, if necessary, batchwise or continuously in a remote plant using ethylene oxide and conventional base catalysts (Schoenfeldt, Surface Active Ethylene Oxide Adducts, Pergamon Press, NY, 1969). Ethoxylated modified OXO alcohols are treated batchwise or continuously using sulfur trioxide as the sulfating agent ("Sulphonation Technology in the Detergent Industry", W. de Groot, Kluwer Academic Publishers, London, 1991). . The product of the preceding step is neutralized with sodium hydroxide to give a modified alkyl ethoxysulfate, sodium salt according to the invention. In a variation of this example, the alkyl chains of the hydrocarbons are varied to produce modified OXO alcohol derived surfactants of the desired chain length as used in the formulation examples. In a further variation, the modified OXO alcohol can be sulfated in the absence of prior alkoxylation.

Example 10

A non-limiting example of a bleach-containing non-aqueous liquid laundry detergent having a composition as described in the following table is prepared:

ingredient weight% Range (% by weight) Liquid phase LAS 25.0 18-35 C24E5 or MBA14.3E5 (Example 9) 13.6 10-20 Solvent or hexylene glycol 27.3 20-30 Spices 0.4 0-1.0 MBA14.4E1S (Example 9) 2.3 1-3.0 Solid phase Protease 0.4 0-1.0 Citrate 4.3 3-6 PB1 3.4 2-7 NOBS 8.0 2-12 lead carbonate 13.9 5-20 DTPA 0.9 0-1.5 Brightener 1 0.4 0-0.6 Silicone antifoam 0.1 0-0.3 Trace ingredients Remaining amount ---

The composition prepared is an anhydrous heavy liquid laundry detergent that provides excellent stain and dirt removal performance when used in standard fabric laundry operations.

Example 11

Liquid detergent compositions are prepared as follows.

A B C D MBA14.4E1S (Example 9) 2 8 7 5 MBA14.4S (Example 9) 15 12 10 8 C24 amine oxide - - - 2 C25AS 6 4 6 8 LMFAA 0-5 0-4 0-3 0-3 C24E5 6 One One One Fatty acid (12/18) 11 4 4 3 Citric acid One 3 3 2 DTPMP One One One 0.5 MEA 8 5 5 2 NaOH One 2.5 One 1.5 Solvent or PG 14.5 13.1 10.0 8 EtOH 1.8 4.7 5.4 One Amylase 0.3 0.3 0.4 0.4 Lipase 0.15 0.15 0.15 0.15 Protease 0.5 0.5 0.5 0.5 Endolase 0.05 0.05 0.05 0.05 Cellulase 0.09 0.09 0.09 0.09 SRP3 0.5 - 0.3 0.3 borax 2.4 2.8 2.8 2.4 A combustible substance - 3 - - Isofol 12 One One One One Silicone antifoam 0.3 0.3 0.3 0.3 Water & trace ingredients Volume to reach 100%

The liquid detergent compositions (A-D) have been found to be very effective for removing a wide range of stains and dirt from fabrics under various conditions of use.

Example 12

The following compositions (E to J) are heavy liquid detergent compositions according to the invention.

Example number E F G H I J MBA14.4E0.8S (Example 9) 17 15 7.0 7.0 12 12 C35E3S / C25E3S 2.0 9.0 - - 7.0 7.0 C25E2.5S - - 12.0 12.0 - - LMFAA 6.0 5.0 0 0 4.0 0 C35E7 6.0 1.0 - - - - C23E9 - - 2.0 1.0 5.0 5.0 APA - 1.5 - 2.0 - 2.5 Fatty acid (C12 / C14) 7.5 1.1 2.0 4.0 5.0 5.0 Fatty acid (C14 / C18) 3.0 3.5 - - - - Citric acid 1.0 3.5 3.0 3.0 3.0 3.0 Protease 0.6 0.6 0.9 0.9 1.2 1.2 Lipase 0.1 0.1 0.1 0.1 0.2 0.2 Amylase 0.1 0.1 0.1 0.1 - 0.1 Cellulase 0.03 0.03 0.05 0.05 0.2 0.2 Endolase 0.1 0.1 - - - - Brightener 2 0.1 0.1 - - - - borax 3.0 3.0 3.5 3.5 4.0 4.0 MEA 8.0 4.0 1.0 1.5 7.0 7.0 NaOH 1.0 4.0 3.0 2.5 1.0 1.0 PG 12.0 12.0 7.5 7.5 7.0 7.0 EtOH 1.0 1.0 3.5 3.5 6.0 6.0 A combustible substance - - 2.5 2.5 - - Trace ingredients Residual amount Residual amount Residual amount Residual amount Residual amount Residual amount

Example 13

The aqueous heavy liquid laundry detergent compositions K to O comprising the heavy chain branched surfactant of the present invention are shown below.

ingredient K L M N O MBA14.4E0.8S (Example 9) 10 12 14 16 20 C25E1.8S 10 8 6 4 0 C23E9 2 2 2 2 2 LMFAA 5 5 5 5 0 Citric acid 3 3 3 3 5 Fatty acid (TPK, RPS or C12 / 14) 2 2 2 2 0 PAE One One 1.2 1.2 0.5 PG 8 8 8 8 4.5 EtOH 4 4 4 4 2 borax 3.5 3.5 3.5 3.5 2 A combustible substance 3 3 2 3 0 pH = 8.0 8.0 8.0 8.0 7.0 Water and trace ingredients Residual amount Residual amount Residual amount Residual amount Residual amount 100% 100% 100% 100% 100%

Example 14

The following aqueous liquid laundry detergent compositions P to T are prepared according to the present invention.

P Q R S T MBA14.4E1S and / or MBA14.4S (Example 9) 1-7 7-12 12-17 17-22 1-35 Any combination of C25E1.8-2.5SC25AS (linear to higher 2-alkyl) C47 NaPSC26 SASLASC26 MES 15-21 10-15 5-10 0-5 0-25 LMFAA 0-3.5 0-3.5 0-3.5 0-5 0-8 C23E9 or C23E6.5 0-2 0-2 0-2 0-2 0-8 APA 0.5 One One 1.5 0.5-2 Citric acid 5 5 5 5 0-8 Fatty acid (TPK, RPS or C12 / 14) 2 2 2 10 0-14 EtOH 4 4 4 4 0-8 PG 6 6 6 6 0-10 MEA One One One One 0-3 NaOH 3 3 3 3 0-7 A combustible substance 2.5 2 1.5 One 0-4 borax 2.5 2.5 2.5 2.5 0-5 Protease 0.5 0.7 0.9 0.9 0-1.3 Lipase 0.0 0.06 0.15 0.3 0-0.3 Amylase 0.15 0.2 0.25 0.3 0-0.4 Cellulase 0.05 0.05 0.2 0.3 0-0.2 PAE 0-0.6 0-0.6 0-0.6 0-0.6 0-2.5 PIE 1.2 1.2 1.2 1.2 0-2.5 PAEC 0-0.4 0-0.4 0-0.4 0-0.4 0-2 SRP 2 0.2 0.2 0.2 0.2 0-0.5 Brightener 1 or 2 0.15 0.15 0.15 0.15 0-0.5 Silicone antifoam 0.12 0.12 0.12 0.12 0-0.3 Water and trace ingredients Residual amount Residual amount Residual amount Residual amount Residual amount Product pH (10% in demineralized water) 7.7 7.7 7.7 7.7 6-9.5

Example 15

To prepare a hard liquid dishwashing detergent composition comprising a modified primary OXO alcohol derived surfactant of the present invention.

ingredient Weight% A Weight% B Weight% C Weight% D MBA13.5E0.6S (Example 9) 5 10 20 30 MBA12.5E9 (Example 9) One One One One C23E1S 25 20 10 0 LMFAA 4 4 4 4 C24 amine oxide 4 4 4 4 EO / PO block copolymers-Tetronic ^R 704 0.5 0.5 0.5 0.5 EtOH 6 6 6 6 Flexible Water (Calcium Xylene Sulfonate) 5 5 5 5 Magnesium ⁺⁺ (added as chloride) 3.0 3.0 3.0 3.0 Water and trace ingredients Residual amount Residual amount Residual amount Residual amount PH @ 10% (when manufactured) 7.5 7.5 7.5 7.5

E F G H I J pH 10% 9.3 8.5 11 10 9 9.2 MBA13.5E0.6S or MBA13.5S (Example 9) 10 15 10 27 27 20 C25PS 10 0 0 0 0 0 LAS 5 15 12 0 0 0 C26 betaine 3 One 0 2 2 0 C24 amine oxide 0 0 0 2 5 7 LMFAA 3 0 One 2 0 0 C11E8 0 0 20 One 0 2 A combustible substance 0 0 0 0 0 5 Diamine One 5 7 2 2 5 Mg ⁺⁺ (as MgCl ₂ ) One 0 0 .3 0 0 Ca ⁺⁺ (as calcium xylene sulfonate) 0 0.5 0 0 0.1 0.1 Protease 0.1 0 0 0.05 0.06 0.1 Amylase 0 0.07 0 0.1 0 0.05 Lipase 0 0 0.025 0 0.05 0.05 DTPA 0 0.3 0 0 0.1 0.1 Citrate 0.65 0 0 0.3 0 0 Water and trace ingredients (To reach 100%)

Example 16

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

K L M N O MBA14.4E0.5S (Example 9) 22 16.5 11 1-5.5 10-25 Any combination of C45ASC45E1SLASC26 SASC47 NaPSC48 MES 0 1-5.5 11 16.5 0-5 QAS 0-2 0-2 0-2 0-2 0-4 C23E6.5 or C45E7 1.5 1.5 1.5 1.5 0-4 Zeolite A 27.8 27.8 27.8 27.8 20-30 PAA 2.3 2.3 2.3 2.3 0-5 lead carbonate 27.3 27.3 27.3 27.3 20-30 Silicate 0.6 0.6 0.6 0.6 0-2 PB 1.0 1.0 1.0 1.0 0-3 Protease 0-0.5 0-0.5 0-0.5 0-0.5 0-0.5 Cellulase 0-0.3 0-0.3 0-0.3 0-0.3 0-0.5 Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-1 SRP 1 0.4 0.4 0.4 0.4 0-1 Brightener 1 or 2 0.2 0.2 0.2 0.2 0-0.3 PEG 1.6 1.6 1.6 1.6 0-2 Sulfate 5.5 5.5 5.5 5.5 0-6 Silicone antifoam 0.42 0.42 0.42 0.42 0-0.5 Water & trace ingredients --- Residue --- Density (g / L) 663 663 663 663 600-700

Example 17

The following laundry detergent compositions P to T are prepared according to the invention.

P Q R S T MBA14.4E0.4S (Example 9) 16.5 12.5 8.5 4 1-25 Any combination of C45ASC45E1SLASC26 SASC47 NaPSC48 MES 0-6 10 14 18.5 0-20 QAS 0-2 0-2 0-2 0-2 0-4 TFAA 1.6 1.6 1.6 1.6 0-4 C24E3, C23E6.5 or MBA14.5E5 (Example 9) 5 5 5 5 0-6 Zeolite A 15 15 15 15 10-30 NaSKS-6 11 11 11 11 5-15 Citrate 3 3 3 3 0-8 MA / AA 4.8 4.8 4.8 4.8 0-8 HEDP 0.5 0.5 0.5 0.5 0-1 lead carbonate 8.5 8.5 8.5 8.5 0-15 Percarbonate or PB1 20.7 20.7 20.7 20.7 0-25 TAED 4.8 4.8 4.8 4.8 0-8 Protease 0.9 0.9 0.9 0.9 0-1 Lipase 0.15 0.15 0.15 0.15 0-0.3 Cellulase 0.26 0.26 0.26 0.26 0-0.5 Amylase 0.36 0.36 0.36 0.36 0-0.5 SRP 1 0.2 0.2 0.2 0.2 0-0.5 Brightener 1 or 2 0.2 0.2 0.2 0.2 0-0.4 Sulfate 2.3 2.3 2.3 2.3 0-25 Silicone antifoam 0.4 0.4 0.4 0-1 Water & trace ingredients --- Residue --- Density (g / L) 850 850 800 850 850

Example 18

The following high density detergent formulations U to X according to the invention are prepared.

U V W X Aggregate C45AS 11.0 4.0 0 14.0 MBA14.3E0.5S (Example 9) 3.0 10.0 17.0 3.0 Zeolite A 15.0 15.0 15.0 10.0 lead carbonate 4.0 4.0 4.0 8.0 PAA or MA / AA 4.0 4.0 4.0 2.0 CMC 0.5 0.5 0.5 0.5 DTPMP 0.4 0.4 0.4 0.4 Spray MBA14.5E5 (Example 9) 5.0 5.0 5.0 5.0 Spices 0.5 0.5 0.5 0.5 Anhydrous additive C45AS 6.0 6.0 3.0 3.0 HEDP 0.5 0.5 0.5 0.3 SKS-6 13.0 13.0 13.0 6.0 Citrate 3.0 3.0 3.0 1.0 TAED 5.0 5.0 5.0 7.0 Percarbonate 20.0 20.0 20.0 20.0 SRP 1 0.3 0.3 0.3 0.3 Protease 1.4 1.4 1.4 1.4 Lipase 0.4 0.4 0.4 0.4 Cellulase 0.6 0.6 0.6 0.6 Amylase 0.6 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 5.0 Brightener 1 0.2 0.2 0.2 0.2 Brightener 2 0.2 0.2 0.2 - Residual amount (water / trace component) 100 100 100 100 Density (g / L) 850 850 850 850

The present invention can use a number of different hydrocarbon feeds as already exemplified herein. Alternative hydrocarbon feeds that may be used in this process include mixtures of certain types of paraffins and / or mono-olefins. These hydrocarbon mixtures can be selected from the following mixtures:

(A) chemical formula Mixture of paraffins:

In the above formula,

The total number of carbon atoms in the branched primary alkyl moieties (including R, R ¹ and R ² branches) of the above formula is 8 to 20, preferably 10 to 20, more preferably about 10 to about 18, and R, R ¹ and R ² are each independently hydrogen, C ₁ -C ₃ alkyl, and mixtures thereof containing trace amounts of impurities such as C ₃ -C ₇ cycloalkyl, aryl, arylalkyl and alkaryl, preferably Is selected from H and C ₁ -C ₃ alkyl (more preferably methyl), provided that R, R ¹ and R ² are not all hydrogen, and when z is 0, one of R or R ¹ is not hydrogen , w, x, y, z are each independently an integer of 0 to 13, provided that the above-mentioned total carbon number and the limitations on w + x + y + z are preferably 8 to 14.

Even more preferred paraffins have only H, methyl, ethyl, propyl or butyl in R, R ¹ and R ² , more preferably only H and methyl, provided that R, R ¹ and R ² are at least one alkyl Includes residues; When present, methyl is present inside, ie as many as possible are removed from the 1-, 2- and preferably 3-carbon positions in the longest countable chain.

Hydrocarbons herein also include mixtures of (B) mono-olefins. These mono-olefins relate to the paraffins of (A) above in the sense that any suitable mono-olefin can be prepared by the dehydrogenation of any of the paraffins of (A) described above (actually, separating the suitable olefins) This can then be dehydrogenated to paraffins). Preferred olefins are mono-olefins, although generally up to about 10% by weight of the olefinic hydrocarbons may be diolefins after dehydrogenation of suitable paraffins.

Like paraffins, the olefins herein can vary widely in structure. For example, possible mono-olefins are as follows:

These structures are, of course, illustrative and are not intended to be limiting.

Hydrocarbons herein also include a mixture of paraffins of (C) (A) and olefins of (B). These hydrocarbon mixtures may be present in any possible combination and may be the result of blending compositions containing only paraffin, only olefins, or any proportion of paraffin / olefin mixture, for example. These mixtures are typically subjected to a specific treatment (eg, fractionation, selective treatment of natural, eg, geologically supplied petroleum feeds such as light crude oil or kerosene, or jet / diesel fuel distilled therefrom). Adsorption, distillation, inclusion, etc.), by separating the desired hydrocarbon mixtures may be derived "essentially" as a result of the hydrocarbons derived from said raw materials. Alternatively, the mixture can be prepared by gradually mixing a more complex mixture from a series of simple hydrocarbons in composition. Hydrocarbon mixtures of the present invention are also known as synthetic conversion processes in petrochemicals such as cracking, hydrocracking, hydroisomerization, hydrogenation, dimerization, dehydrogenation, isomerization, It can be derived from the disproportionation process. Equivalent compositions may also be more laboriously prepared by including known organic synthetic schemes, eg, Grignard reactions. Catalytic isomerization on zeolites and modified zeolites can be particularly useful.

Hydrocarbon mixtures useful herein may further include the following mixtures:

(D) a mixture of paraffins of (A) and other known olefins and / or paraffins (particularly linear) having the same or less preferably different carbon number range with the olefins of (B).

In addition, the hydrocarbons herein include the following mixtures:

(E) A mixture of (A) to (D) with benzene or non-aliphatic hydrocarbonation. This includes the use of other solvents such as cyclohexane, pentane, toluene and the like.

Particular groups of preferred paraffins have formulas selected from formulas II, III, and mixtures thereof:

Formula II

Formula III

In the above formula,

a, b, d and e are integers, a + b is 10-16, d + e is 8-14, wherein further

when a + b = 10, a is an integer from 2 to 5, b is an integer from 5 to 8,

when a + b = 11, a is an integer from 2 to 5, b is an integer from 6 to 9,

when a + b = 12, a is an integer from 2 to 6, b is an integer from 6 to 10,

when a + b = 13, a is an integer from 2 to 6, b is an integer from 7 to 11,

when a + b = 14, a is an integer from 2 to 7, b is an integer from 7 to 12,

when a + b = 15, a is an integer from 2 to 7, b is an integer from 8 to 13,

when a + b = 16, a is an integer from 2 to 8, b is an integer from 8 to 14,

when d + e = 8, d is an integer from 2 to 7, b is an integer from 1 to 6,

when d + e = 9, d is an integer from 2 to 8, b is an integer from 1 to 7,

when d + e = 10, d is an integer from 2 to 9, b is an integer from 1 to 8,

when d + e = 11, d is an integer from 2 to 10, b is an integer from 1 to 9,

when d + e = 12, d is an integer from 2 to 11, b is an integer from 1 to 10,

when d + e = 13, d is an integer from 2 to 12, b is an integer from 1 to 11,

When d + e = 14, d is an integer from 2 to 13, b is an integer from 1 to 12.

The hydrocarbon composition of the present invention is characterized in that one or more ether or alcohol oxygen atoms are present in the carbon chain or are blocked by the carbon chain (so-called "oxygenated" impurities) or aryl, arylalkyl or alkaryl is attached to the carbon chain as a branch. Varying the amount of impurities, such as impurities present, or impurities in which quaternary carbon atoms are present, or diolefins, or impurities attached to adjacent carbon atoms (up to about 20%, preferably less than about 1%) Can provide. Such impurities are of course undesirable. It is particularly desirable to limit impurities known to adversely affect biodegradation or to produce odors. For the largest mass efficiency, the minimum total carbon content is present in any side chain, provided that the resulting hydrocarbons preferably further have one or more carbon atoms in the side chain. Preferred paraffins and / or olefins herein contain varying amounts of nonalkylbenzene aromatic, cycloalkyl and alkyl cycloalkyl impurities, but they are more preferably removed by known adsorption steps. Preferred paraffins and / or olefins may contain certain sulfur and / or nitrogen, but they may produce an unpleasant odor, and for this or other reasons, desulfurization and well known in the petroleum industry And / or they are preferably removed by a nitrogen removal technique.

Preferred olefins are closely related to the paraffins described above: they have a structure formed by dehydrogenation of the paraffins in accessible positions to form the corresponding mono-olefins. Particular preference is given to monomethyl-branched and dimethyl-branched, especially monomethyl-branched mono-olefins.

It is to be understood and appreciated that the inherent concepts taught herein for selecting preferred paraffins and olefins for desirable results include several features, including the following features:

(a) carefully selecting a mixture of C10-C18 hydrocarbons, typically with one or two alkyl substituents, which are as short as possible and at least located in a manner that avoids biodegradation problems; And

(b) preferably has at least some methyl residues not present at the 2-position of the longest hydrocarbon chain.

Without wishing to be bound by theory, certain more complex mixtures within the defined range form hydrophobic materials for "modified" surfactants that are particularly water soluble, hardness resistant and well soluble in cold water, including alkylbenzenes and oxo alcohols. It is considered to have particularly good properties.

In addition, these hydrocarbon mixtures can be widely used in the preparation of modified surfactants. These can be used to prepare modified alkyl sulfates, alkyl alkoxylates, alkylalkoxy sulfates or alkylaryl sulfonates such as alkylbenzene sulfonates. Alkyl sulfates, alkyl alkoxylates, alkylalkoxy sulfates are prepared by first converting the hydrocarbon mixture to the corresponding alcohols and then optionally sulfating and / or alkoxylating the alcohols. The alcohol can be formed by conventional methods, for example by an oxo process. Similarly, sulfation and / or alkoxylation can be carried out by conventional methods. Alkylbenzene sulfonates are formed by alkylating benzene with an olefin containing hydrocarbon mixture and then sulfated the resulting alkylbenzene. The resulting alkyl benzene sulfonate is the so-called "modified alkyl benzene sulfonate".

Claims (3)

Providing a hydrocarbon feed comprising a branched aliphatic hydrocarbon having 8 to 20 carbon atoms; This hydrocarbon feed can be partially or wholly used, using a porous medium. At least one branched hydrocarbon-rich stream comprising increased proportions of branched acyclic hydrocarbons relative to the hydrocarbon feed, and optionally at least one A linear hydrocarbon-rich stream comprising an increased proportion of linear aliphatic hydrocarbons relative to the hydrocarbon feed and Adsorbing to an outlet stream comprising cyclic and / or aromatic and / or ethyl- or higher higher alkyl-branched hydrocarbons, wherein the hydrocarbons in these layers as well as one or more layers retaining a porous medium (A) characterized in that a simulated moving bed adsorptive mean is used comprising a simulated transfer device of a porous medium countercurrent to a stream, (I) and optionally dehydrogenation of the branched hydrocarbon-rich stream of step (A) partially or wholly to form an olefinic branched hydrocarbon-rich stream comprising mono-olefins. Treating the olefinic branched hydrocarbon-rich stream to reduce the content of diolefinic impurities (ii) and (B) comprising at least one of (iii) treating the olefinic branched hydrocarbon-rich stream to reduce the content of aromatic impurities, At least one step (B ′) in which the product of step (B) is reacted with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst, Optionally, the mono-olefins in the olefinic branched hydrocarbon-rich stream of step (B) are known adsorbents or porous media, provided that the adsorbent or porous medium is different from the porous medium of step (A), and that the olefin / paraffin separation (C) partially or wholly concentrated by adsorptive separation means, and optionally, simultaneously recycling the paraffins to the dehydrogenation step (B) and Reacting the olefinic branched hydrocarbon-rich stream produced in step (B ′) or optionally further concentrated in step (C) with carbon monoxide and hydrogen in the presence of an OXO catalyst to form a modified alkylbenzene (D Method for producing a modified alkyl benzene comprising a). 2. The process of claim 1, wherein the internal isomer selectivity of the alkylation catalyst is 0 to 40. 3. A process according to claim 1, characterized in that means are provided for feeding the product of step (C) to step (D) or to the alkylation step or to both of them in parallel.