CN1325372A - Improved processes for making surfactants via adsorptive separation and products thereof - Google Patents

Abstract

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

Description

Improved process for preparing surfactants by adsorption separation and products thereof

Field of the invention

The present invention relates to the preparation of various surfactants useful in cleaning products. The preferred method involves the use of specific equipment and specific combinations of adsorptive separation steps to separate certain hydrocarbons. Preferably, these devices include two or more special adsorption beds and two or more special types of rotary valves and various special types of porous adsorbents (which have a pore size larger than that used in conventional linear alkylbenzene production. Various combinations of agent pore size). Preferred methods also use specific alkylation steps with specific internal isomer selectivity, or specific OXO reaction steps. The invention also relates to the products of these processes (including certain modified alkylbenzenes), modified alkylbenzene sulfonate surfactants, detergent alcohols and surfactants derived therefrom, and household cleaning products (especially containing various laundry detergents of these products). The preferred process herein employs an unconventional sequence of adsorption separation steps to ensure that certain branched hydrocarbon moieties are obtained, which are then reused as alkylating agents in additional process steps for the production of aromatics or other useful surfactants, Such as OXO reaction to form special detergent alcohols, followed by alkylation, sulfation or similar steps. Surprisingly, these fractions can even be obtained from the effluents currently produced in the production of linear alkylbenzenes.

Background of the invention

Various highly branched alkylbenzene sulfonate surfactants, such as those based on tetrapolypropylene (known as "ABS" or "TPBS"), have been used in detergents in the past. However, we found that the biodegradability of these surfactants was rather poor. Processes for the production of alkylbenzene sulfonates have been modified over a long period of time to make them as linear ("LAS") as practical. A major part of most of the technology for producing shaped alkylbenzene sulfonate surfactants involves this goal. Today, the large-scale industrial production of alkylbenzene sulfonates used in the United States involves linear alkylbenzene sulfonates. But linear alkylbenzene sulfonates are not without limitations, for example, improved performance for hard water cleaning would be more desirable.

Various methods have recently been developed in the petroleum industry, such as various methods for the production of low-viscosity lubricating oils or high-octane gasoline. These inventors' discoveries are how to delinearize various hydrocarbons. Reaching a limited and controlled level provides new and useful insights. But this delinearization in question is not characteristic of various industrial processes in different fields of production of alkylbenzenesulfonate surfactants for household products at present. It is not surprising that the preparation of linear compounds does not involve delinearization from the extensive teaching in the field of surfactants according to LAS.

Most of the industrial processes for the preparation of various alkylbenzenes rely on the HF or aluminum chloride catalyzed alkylation of benzene. Not long ago it was discovered that certain zeolite catalysts could be used in the alkylation of benzene with olefins. Such a process step is described in the literature of other conventional processes for the production of shaped alkylbenzene sulfonates. For example, UOP's ^DETAL® process uses zeolite alkylation catalysts. We believe that the DETAL ^- process and all other present day commercial processes for the production of alkylbenzene sulfonates are unable to meet the requirements for internal isomer selectivity of the preferred process of the present invention and the alkylation catalysts defined hereafter. Furthermore, we also believe that the ^DETAL® process catalyst (or various catalysts) does not have the intermediate acidity and intermediate pore size of the alkylation catalysts used in the preferred process of the present invention. Other recent publications describe the use of mordenite as an alkylation catalyst, but even such publications fail to provide the specific combination of process steps required by the present invention. Additionally, in view of the linearity required in the alkylbenzene sulfonate products of conventional known processes, they also typically include various processes involved in providing or producing substantially linear rather than delinearized hydrocarbons prior to alkylation. kind of steps. Other possible exceptions are described in US 5,026,933 and US 4,990,718. From a detergent industry point of view, these and other known processes have limitations in terms of cost, catalysts, large fractions of distillation that require purge or non-detergent use substances in the propylene oligomerization or olefin dimerization stages and The limited range of product compositions, including the mixture of chain lengths available, has a number of disadvantages. In short, these advances made by the petroleum industry are not optimal from the point of view of a professional formulator of detergent products.

It is known in the art to employ specific adsorption separation methods for the production of linear alkylbenzenes (see US 2,985,589). However, the methods described so far do not lead to branched alkylbenzenesulfonates.

It is known in the art to prepare various long chain methyl paraffins for use as industrial solvents by various methods including urea clathration and separation over "molecular sieves". See Chemical Abstracts, 83:100693 and JP 49046124 B4. The process is said to involve a double urea addition, such as treating the petroleum fraction once with urea to remove n-alkanes as complexes, and then using an excess of urea a second time to obtain mixed n-alkanes and long monomethyl chains. Adducts of alkanes. While this method may have some limited applicability and may generally be included in the general method of the invention, its limitations are significant. Although this method was introduced in 1974, to date it has not been incorporated into any overall process for the preparation of various surfactants such as the modified alkylbenzene sulfonates described herein.

It is also well known how to prepare various OXO alcohols and thus surfactants, as will be further described in the background section hereafter. However, currently available OXO alcohols have several disadvantages such as less solubility at a given chain length than is increasingly required for low-temperature washes in the production of surfactants, or reliance on more expensive methods such as olefinic Oligomerization, isomerization and disproportionation reactions; or still have a high content of linear species.

Background technique

The following documents can be used as the background of the present invention: WO 97/39090, WO 97/39087, WO 97/39088, WO 97/39091, WO 98/23712, WO 97/38972, WO97/39089, US 2,985,589; Chemical Abstracts, 83 : 100693; JP 49046124B4 12/07/74; EP 803,561 A2 10/29/97, EP 559,510 A 9/8/93; EP 559,510B1 1/24/96; US 5,026,933; US 4,990,718; US 4,855,527; US 4,870,038; US 2,477,382; EP 466,558,1/15/92; EP469,940,2/5/92; FR 2,697,246,4/29/94; US 3,196,174；US 3,238,249；US 3,355,484；US 3,442,964；US 3,492,364；US 4,959,491；WO 88/07030,9/25/90；US 4,962,256；US 5,196,624；US 5,196,625；EP 364,012 B,2/15/90；US 3,312,745 ；US 3,341,614；US 3,442,965；US 3,674,885；US 4,447,664；US4,533,651；US 4,587,374；US 4,996,386；US 5,210,060；US 5,510,306；WO 95/17961,7/6/95；WO 95/18084；US 5,510,306；US 5,087,788 US 4,301,316; US 4,301,317; US 4,855,527; US 4,870,038; US 5,026,933; EP 559,510A and B of the cited documents are particularly concerned with the production of high octane gasoline by recycling the stream to the isomerization reactor. The grafted porous materials of EP 559,510 as well as the grafting of zeolites (eg by tin alkyls) can be used in the present invention. US 5,107,052 also relates to improving the octane number of gasoline and describes the separation of C4-C6 methyl paraffins using various molecular sieves such as AIPO4-5, SSZ-24, MgAPO-5 and/or MAPSO-5 containing less than 2% water . These molecular sieves are said to selectively adsorb dimethyl paraffins but not monomethyl and n-paraffins.

The production of alkylbenzene sulfonate surfactants has recently been reviewed. See Volume 56 in the series "Surfactant Science", Marcel Dekker, New York, 1996, specifically including Chapter 2 entitled "Alkylaryl Sulfonates: History, Production, Analysis and Their Environmental Properties", 39- At 108 pages, the chapter includes 297 references. This work provides a large number of references describing various methods and process steps such as dehydrogenation reactions, alkylation, distillation of alkylbenzenes, etc. See also "Detergent Alkylate" in the Encyclopedia of Chemical Processing and Design, Eds. Mc. Ketta and Cunningham, Marcel Dekker, NY, 1982, specifically at pp. 266-284. Various adsorption methods such as UOP's Sorbex method and other related methods are also described in Kirk Othmer's Encyclopedia of Chemical Technology, 4th Edition, Volume 1, see "Adsorption and Liquid Separation", including pages 583-598 and cited therein references. See also various publications of UOP Corp., including "Processing Guide" available from UOP Corp., Des Plaines, Illinois. Methods for industrial paraffin isolation and separation using molecular sieves include ^MOLEX_ (UOP Inc.) in liquid phase and ISOSIV (Union Carbide Corp.) and ^ENSORB_ (Exxon Corp.) and TSF_ or Texaco Selective Finishing in vapor phase Law. All of these methods are believed to employ 5 Angstrom molecular sieves as the porous media. The operating temperature, pressure and other operating conditions and equipment not mentioned here are conventional, that is, well known and defined in the literature of producing shaped alkylbenzene sulfonate surfactants. of those. Each document herein is incorporated by reference in its entirety.

US 3,732,325, issued May 8, 1973, describes a process for the adsorptive separation of aromatic hydrocarbons.

US 3,455,815 issued July 15, 1969, US 3,291,726 issued December 13, 1966, 3,201,491 issued August 17, 1965, and US 2,985,589 issued May 23, 1961 describe Similar to the moving bed adsorption separation method.

US 5,780,694, issued July 14, 1998, and WO 98/23566, issued June 4, 1998 (herein incorporated by reference) relate to certain branched chain detergent alcohols and surfactants derived therefrom. These documents include descriptions of the well known OXO process and catalysts suitable for carbonylation. See paragraphs 10 and 11 on page 694 for details.

US 5,510,564, issued April 23, 1998 (hereby incorporated by reference) describes the purification of hydrocarbons, particularly the removal of aromatics.

US 5,276,231, issued January 4, 1994, describes the removal of aromatics from hydrocarbons by sulfolane extraction.

US 4,184,943, issued January 22, 1980, describes the separation of adsorbed hydrocarbons.

US 4,006,197, issued February 1, 1977, describes the adsorptive hydrocarbon separation of normal paraffins.

US 5,220,099, issued June 15, 1993 and US 5,171,923, issued December 15, 1992, describe the adsorption removal of aromatics, sulfur, nitrogen and oxygen containing compounds by magnesium Y or Na-X zeolites and colored entities.

In 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", pp. 11-86 Pages provide a general background including the OXO process (see page 71 et seq.) and certain feedstocks (see page 60 et seq.). It is to be noted that this reference on page 65 et seq. entitled "Branched Chain Olefins" does not describe branched chain alkenes suitable for use in the methods of the present invention - the identified "branched chain" alkenes are biologically unsuitable The "hard" type. The OXO process described on page 72 and following converts linear olefins to "branched" and linear aldehydes and/or alcohols. In addition, this use of the term "branched chain" differs from the method of the present invention which employs at least part of the feedstock of the methyl branch on the mid-chain as the primary source of branching, where the OXO reaction provides specific methyl branched primary alcohols of which only The second aspect of any branching is from the OXO reaction.

The ^UOPOLEX® process and the adsorbents used therein are described in the aforementioned references and references cited therein, respectively, see eg pages 60-63 referring to Cu- or Ag-doped zeolites. See US 3,969,276 (Zeolite X or Y doped with silver) issued July 13, 1976 for more details. See also DB Broughton and RC Berg, Hydrocarbon Process, Vol. 48(6), 115 (1969); DB Broughton and RC Berg, Technical Report AM-69-38, National Petroleum Refiners Association, 1969 Annual Meeting (March 23, 1969) ; DB Broughton and RC Berg in Chemical Engineering (January 26, 1970) p. 86 (entitled "Two approaches to the synergistic preparation of linear monoolefins").

The fourth edition of Kirk Othmer's Encyclopedia of Chemical Technology, Vol. 1, pp. 893-913 (1991) (titled "Alcohols, Higher Aliphatic Compounds", subtitled "Synthetic Methods") describes the reaction of OXO to form detergent alcohols , see "Modified Cobalt Catalyst, One-Step Low-Pressure Process" (pp. 904-906) for details. Note again that the illustrated methyl branched alcohols (see e.g. p. 904) can only be generated from linear precursors, and that the OXO-branch is at the 2-position (as in references mentioned above).

See also Surfactant Science Series, Vol. 56 "Anionic Surfactants" (Marcel Dekker, N.Y., Ed. W. Linfield, 1996, Chapter 1 "Raw Materials for Nonionic Surfactant Synthesis" pp. 1-142 , incorporated herein by reference) also describes feeds commonly used in detergent preparation, describes known methods for adsorption and other separations, describes alkylation of detergents and describes OXO or carbonylation process steps ( See eg pages 23-25).

The literature on the OXO method also includes "A New Synthesis Using Carbon Monoxide" (Ed. J. Falbe, Springer-Verlag, New York, 1980).

Commercial processes for the preparation of detergent alcohols other than those available here should now be understood to include the sequence of separation of linear paraffins from kerosene by adsorptive separation, dehydrogenation to linear internal olefins by the ^PACOL® process (or similar) , by the OLEX_ method (or similar) and OXO, in one of two ways (via conventional OXO catalysts to 2-alkyl substituted primary alcohols such as ENI's LIAL_alcohols, or to isomerize alkenes to the terminal position followed by terminal OXO addition (eg Shell/Mitsubishi method)) to separate alkenes from alkanes.

See also WO 97/01521A1 published January 16, 1997 and 95 ZA-0005405 published June 25, 1995. See also the various technical bulletins and publications of Sasol and/or Sastech in South Africa, particularly relating to known or available OXO alcohols prepared or producible by the OXO process belonging to these companies.

Brief description of the drawings

1-18 are schematic illustrations of some methods according to the invention. Figure 8 shows more clearly the structure of two adsorptive separation units, each of the type seen in the first two-stage adsorptive separation step of Figures 1 and 2 respectively. Note that the connections of FIG. 8 are like those shown in FIG. 1 , but different from those shown in FIG. 2 .

Solid lines are used to represent major process steps and process flows. Dashed lines represent steps and streams that may not be necessary in the various processes but are present in various preferred process embodiments. Rounded rectangles represent individual process steps, stages or units. Lines with numbers represent feeds, intermediate process streams and products. "SOR" means Sorptive Separation Step. "4/5" means that small pore diameter zeolites, especially Ca zeolite 5A (quite commonly used in linear alkylbenzene production) are used for adsorption separation. "5/7" indicates that various porous materials such as SAPO-11 or any equivalent porous material with the ability to adsorb the following substances are used for adsorption separation:

· Monomethyl branched paraffins and/or

· Monomethyl branched monoolefins and/or

· Non-gem dimethyl alkanes and/or

·Non-gem dimethyl olefins

However, gem-dimethyl hydrocarbons, cyclic (five, six or greater number of rings) hydrocarbons or higher branched hydrocarbons (whether aromatic or aliphatic) are excluded. The term "gem dimethyl" as used herein means having two methyl groups attached to one internal carbon atom of a hydrocarbon, such as:

Here only the adsorption stage SOR 4/5 and/or the adsorption stage SOR 5/7 are of the type for stage (a) of the preparation of modified alkylbenzenes or stage (A) of the preparation of modified primary OXO alcohols as described below .

Here the porous material with large pore size should not adsorb such hydrocarbons. The phase reaction adsorbs the following various hydrocarbons. The following examples illustrate what is meant by the term "non-gem-dimethyl" hydrocarbons:

Note that any methyl moieties at the ends of the backbone are not included within the definition of "non-gem-dimethyl" as used herein. In addition, consistent with this regulation, the underlying hydrocarbons should be adsorbed by large-pore porous materials. It is a "monomethyl" hydrocarbon:

Large pore size porous materials suitable for use herein are described more fully and more fully in the specification hereinafter. "DEH" refers to a step in which the stream undergoes at least partial dehydrogenation (partial dehydrogenation is common in conventional linear alkylbenzene production, although complete dehydrogenation may also be employed here), and "ALK" refers to the alkylation step . Any step, stage or unit represented by a rounded rectangle may in practice include only the main step, or more generally may include one or more additional steps, which are optional in the present invention, or only in the In the preferred embodiment is the main. Such additional steps not shown in the figures include, for example, various types of distillation steps commonly employed in the practice of the art.

In Figures 9-18, the presence of "DIST" refers to a distillation step, and the presence of "SORO/P" refers to the adsorption olefin/paraffin separation step, such as for the production of modified primary OXO alcohols which will be described in detail hereafter The stage (c) of the UOP ^OLEX_ process, where "OXO" is present refers to the carbonylation step. Such process steps are well known in the art: see the "Background" section.

With the above provisions in place, it can be seen that Figure 1 exemplifies a process with two sequential adsorption separation steps (collectively according to the invention hereinafter defined adsorption separation stage (a)), followed by a dehydrogenation step (step (b) thereafter); optionally followed by an alkylation step (step (c) thereafter). Although step (c) is optional in the broad sense of the present invention, it is present in all preferred embodiments involving the preparation of modified alkylbenzenes according to the present invention, and when preparing modified alkylbenzene sulfonates Surfactants are usually followed by (d) sulfonation steps, (e) neutralization and (f) blending to formulate household cleaning products. Steps (d)-(f) employ various conventional means and are not shown in Figures 1-8.

In the process of Figure 1, the hydrocarbon feed 1 is sent to a first adsorptive separation step employing a 4-5 Angstrom zeolite bed, for example a step according to US 2,985,589. The linear hydrocarbon stream is discharged as discharge stream 6 . As a comparison, stream 6, which contains a large proportion of linear hydrocarbons in conventional linear alkylbenzene production, would be sent to DEH without step SOR 5/7 and associated various streams. In the process according to the invention according to FIG. 1 , the intermediate-rich branched hydrocarbon stream 2 is retained and sent to a second adsorptive separation step. The second adsorptive separation step employs a specific type of porous media and produces a branch-rich stream 3 (product of stage (a) defined hereafter) entering the dehydrogenation reactor (DEH) and an effluent stream 7 . A particular type of porous media that is preferred is a "large pore" zeolite, where such zeolites are characterized by pore sizes that are larger than those of zeolites used in the production of linear alkylbenzenes, most preferably having a pore size of greater than about 5 angstroms to about 7 angstroms. Angstroms (although larger porous materials can be used), and the pore size can be "tuned down" by using, for example, alkyl tins. Stream 4 represents dehydrogenated branched-rich hydrocarbons and stream 8 represents recycled branched alkanes. Also illustrated is the alkylation step included in the preferred embodiment of the invention according to the invention. The effluent from the alkylation step is a modified alkylbenzene as defined elsewhere herein.

Figure 2 is a schematic diagram of the various steps in another embodiment of the method of the present invention. Although generally similar to the method of FIG. 1 , the method of FIG. 2 has a major difference, specifically, the pore size of the adsorption bed is reversed in the adsorption separation step.

Figure 4 is a schematic representation of one embodiment of the present invention starting with a hydrocarbon feed 23 such as from a conventional linear alkylbenzene production process or from a side waste stream of a conventional linear detergent alcohol process. An effluent stream 27 and a branch-enriched stream 24 are obtained using an adsorption separation step using specific porous media. The latter is dehydrogenated in the step labeled DEH. Preferably, this particular type of porous media is a zeolite having a pore size larger than that of the zeolite used to make the linear alkylbenzenes, most preferably a pore size greater than about 5 Angstroms to about 7 Angstroms. The dehydrogenated hydrocarbon stream 25 is sent to the alkylation step ALK, from which a modified alkylbenzene product 26 is sent. The optional recycle stream is indicated as 28.

Figure 3 is a schematic diagram showing an embodiment of the invention similar to Figure 4 but employing substantially different feed and intermediate process stream compositions. For example, Figure 3 utilizes a C10-C14 paraffin fraction with a fixed ratio of linear/branched paraffins as feed 17 from which various cyclic compounds, aromatics, gem-dimethyl-, ethyl- Or higher branched hydrocarbons than ethyl.

When comparing Figure 3 with Figure 4 it can be seen that since the outline of the step structure is the same, the method exemplified is the same. The difference is that quite different results are obtained by varying the hydrocarbon feed. Figure 4 uses a waste liquid stream from a linear alkylbenzene production facility as hydrocarbon feed 23 to obtain predominantly branched modified alkylbenzene 26. The process of Figure 4 can be set up as an "add-on" process to a standard linear alkylbenzene production plant. In contrast, Figure 3 employs a mixture of linear and branched alkanes inherent in unprocessed jet/diesel from kerosene, linear alkylbenzene production facilities, as the hydrocarbon feed. The process of Figure 3 results in 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 set up as a "stand-alone" plant without connection to a conventional linear alkylbenzene production plant. These observations are only used to better illustrate the method and should not be considered as limiting conditions.

Figures 5, 6 and 7 are schematic representations of other embodiments of the invention for regulating other different hydrocarbon feeds. More specifically, these figures illustrate various methods of regulating mixed paraffin/olefin feeds.

Figure 8 shows in more detail the structure of the particular adsorptive separation seen in other process schematics such as Figures 1 and 6. Each box represents an adsorption separation unit. The vertical arrangement of adsorption separation beds (AC on the left of each section) in each block is controlled by rotary valves (RV). Adsorption separation is accomplished by distillation in columns RC and EC. The streams marked "feed", "extract" and "raffinate" in the leftmost adsorption separation correspond to the streams marked "1", "6" and "2" in Fig. 1 . The raffinate stream of the first adsorptive separation (without the extract as in the case of conventional linear alkylbenzene production) becomes the feed for the second adsorptive separation. The raffinate of the second adsorption separation in FIG. 8 corresponds to stream 7 in FIG. 1 . The extract of the second adsorption separation in Fig. 8 corresponds to stream 3 in Fig. 1: this is the dehydrogenated and/or alkylated stream obtained in the process of the present invention.

As mentioned above, FIG. 8 also illustrates in more detail the case of a single adsorptive separation here. Thus, although connections are not shown in any of Figures 2, 3, 4, 5, and 7, appropriate interconnections of the specific elements shown in the two blocks of Figure 8 can represent Figures 2, 3 in more detail , 4, 5 and 7 for any single adsorption separation case.

The following conventions are used in Figures 1-7: those leaving above the adsorptive separation marked "SOR" represent the fraction of hydrocarbons adsorbed by porous media, and those leaving below the adsorptive separation marked "SOR" represent the fraction of slip adsorbed part. The portion that exits "upper" is sometimes referred to in the art as "adsorbate" or "extraction," while the portion exiting "below" is sometimes referred to as "raffinate" or waste. The terms "above" and "below" are used herein to facilitate reading method schematics, but should not limit practice of the method of the present invention to any particular geometric arrangement.

Using similar principles to those used for Figures 1-8, Figure 9 illustrates a process for the production of modified primary OXO alcohols using, as intermediates, medium chain methyl branched endenes having a number of carbon atoms suitable for detergent applications, wherein OXO The catalyst preisomerizes a large amount of internal alkenes to α-olefins, followed by oxo synthesis mainly on the terminal carbon atoms. More specifically, the crude hydrocarbon feed 51 is distilled using distillation column DIST to ensure that the hydrocarbon feed is suitable for the remainder of the process. Feed 1 may ideally be a narrower carbon range paraffin cut. A light cut 52 and a heavy cut 53 were also obtained, but could not be further used for the preparation of the OXO alcohols of the invention. The hydrocarbon feed 1 is passed through a simulated moving bed adsorption separation system comprising units SOR 4/5 followed by SOR 5/7, each unit being suitable for the MOLEX_type, connected in the order shown. The structure is set so that a linear-rich stream (adsorbate) rich in linear paraffins and designated 6 in Figure 9 is withdrawn from unit SOR4/5. A branched intermediate stream (raffinate) 2 rich in methyl branched paraffins enters unit SOR 5/7. Vent stream 7 from SOR 5/7 containing unwanted cyclic, aromatic, ethyl branched and higher branched paraffins is discarded. The enriched branch stream 3 from SOR5/7 so far is a purified methyl branched paraffinic stream and enters a dehydrogenator DEH (e.g. PACOL_type), where up to 20% of the paraffinic stream is mainly converted to the corresponding mono alkene. The enriched side stream (olefin stream) 4 containing said monoenes as well as unreacted paraffins and some diene impurities enters the SOR O/P, which is a simulated moving bed adsorption separation system designed using OLEX_ or Alkenes are separated from paraffins in a similar manner. For example a suitable adsorbent is copper or silver on zeolite X or Y. The purified olefinically rich side stream (adsorbate) 55 from the SOR O/P (mostly methyl branched olefins by now) is fed to the OXO reactor. The recycle stream 8 is mainly methyl branched paraffins. OXO reactors are designed for what is known in the art as the "one-step low-pressure OXO process" in which a catalytic metal other than iron is used that is modified with a bulky phosphine ligand (see references in Background) . The crude modified primary OXO alcohol (product stream 58) is separated from the recyclable material by distillation and other auxiliary methods (not shown) and the cleaned modified primary OXO alcohol is thus separated from the recyclable material Called stream 57. See the table below for a more detailed description of the composition of the individual streams.

Figure 10 is similar to Figure 9 except that it incorporates one or more process steps after the dehydrogenation step to hydrogenate the diene impurity produced in the dehydrogenator and convert it to monoene. This is a typical DEFINE_ type phase of UOP Corp registration. There is also one or more other aromatics removal steps, such as UOP's PEP_ process, mainly for aromatic impurities formed during the dehydrogenation process.

Figure 11 is similar to Figure 10 except that it uses a simplified approach: a mixture of olefins and paraffins is used as the feed to the OXO reactor, so far recycle stream 8 is the main part (>70%) of the output of the OXO reactor.

Figure 12 is similar to Figure 10, except that cells SOR 4/5 and SOR 5/7 have the opposite structure.

Figure 13 is similar to Figure 11, except that cells SOR 4/5 and SOR 5/7 have the opposite structure.

Figure 14 is similar to Figure 12, except that SOR 4/5 was removed so that a mixture of linear and methyl branched compounds was used throughout the method. The final product is a mixture of linear and methyl branched primary OXO alcohols.

Figure 15 is similar to Figure 13, except that SOR 4/5 was removed so that a mixture of linear and methyl branched compounds was used throughout the method. The final product is a mixture of linear and methyl branched primary OXO alcohols.

Figure 16 is similar to Figure 10, except that the apparatus is configured so that the olefinically rich branched stream 55 can be used to produce modified alkylbenzenes and/or modified primary OXO alcohols.

Figure 17 is similar to Figure 11, except that the apparatus is configured so that methyl branched olefin stream 54 can be used to produce modified alkylbenzenes and/or modified primary OXO alcohols.

Figure 18 is similar to Figure 14, except that the apparatus is configured such that methyl branched and linear olefin stream 61 can be used to produce products containing modified alkylbenzenes and/or modified primary OXO alcohols as well as the corresponding linear counterparts .

SUMMARY OF THE INVENTION

In a preferred embodiment, the present invention relates to a process for the preparation of modified alkylbenzene sulfonate surfactants or modified primary OXO alcohols and surfactants derived therefrom, or even mixtures of these different types of surfactants . The process of the invention begins with a hydrocarbon feed as defined in more detail elsewhere herein. "Modification" refers to a very specific type of branching. Specifically, eg, in OXO alcohols throughout, "modification" refers to methyl branching at positions other than ordinary OXO, while substantially avoiding branching positions or types that affect biodegradation. Preferably "modified" refers to mid-chain positions, mono-lower alkyl, especially monomethyl substituted OXO alcohols. The process comprises (a) a specifically defined adsorption separation stage and (c) an alkylation stage when producing modified alkylbenzenes and/or alkylbenzene sulfonates. Particularly useful to detergent producers, the hydrocarbon feed can be the adsorption separation raffinate or waste stream from a linear alkylbenzene production process or a conventional linear detergent alcohol process, although other feeds such as Shell Brown Carbon/Diesel or Olefin.

When the feed is a paraffin, embodiments of the process of the invention usually and preferably also include (b) a dehydrogenation stage inserted between the adsorption separation and alkylation sequence and, when modified alkylbenzenes are desired The product of (c) an alkylation stage. Clearly the dehydrogenation process is not essential when the feed is olefins. In general, the alkylation stage is preferably followed by (d) sulfonation, (e) neutralization and (f) formulation into household cleaning products by mixing, agglomeration, coagulation, spray drying, etc. Any stage can have more than one step and include various options such as distillation, provided it includes at least the specified minimum units.

When producing modified alkylbenzenes, stage (a) adsorptive separation comprises at least partial separation of a hydrocarbon feed selected from olefin feeds, paraffin feeds and mixed olefin/paraffin feeds to comprise at least one relative to a branched-rich stream having an increased proportion of branched acyclic hydrocarbons relative to the hydrocarbon feed (eg, greater than at least about 50% relative to at least about 10% by weight in absolute terms), and typically One or more other streams, such as comprising an increased proportion of linear acyclic aliphatic hydrocarbons relative to the hydrocarbon feedstock (such as at least about 50% in relative terms, at least about 10% in absolute terms ( weight)) of at least one linear-rich stream. Other streams present in the process may vary in composition. Such streams include effluent streams in which cyclic and/or aromatic undesirable components from the feed are generally present in higher amounts than in the feed, recycle streams, and the like may also be present.

More specifically, the adsorptive separation part (a) of the process of the present invention has one or more steps, comprising first providing a hydrocarbon feed, and then at least one step selected from adsorptive separation using porous media (preferred), using a method selected from urea , thiourea, and alternatively caged amide cage compounds, and various combinations thereof. This stage employs a simulated moving bed adsorption separation unit known in the art (see in particular US 2,985,589, incorporated herein in its entirety), which includes at least one bed supporting the porous media or clathrate compound (see, for example, US 2,985,589 Fig. 1 and associated instructions) and the means in the bed for simulating the movement of the porous media or clathrate compound countercurrent to the hydrocarbon stream, usually a highly specialized rotary valve (see in particular US 2,985,589 Figure 2).

What is particularly unusual and novel in the process description of the present invention is that the moving bed adsorption separation simulated here is minimally used to extract the mainly branch-rich stream, i.e. exactly the same as that used on the linear alkylbenzene sulfonate surface. The practice for active agent production is the opposite. This major difference is also associated with beds having a different composition (compared to conventional practice), that is, at least one bed containing a different 4-5 Angstrom zeolite (commonly used in linear alkylbenzene production), by Have larger aperture sizes and reconfigure process equipment (in particular the bed and the equipment) so that they are connected differently to the relevant process steps. More specifically, these devices are constructed so that branched streams are passed through the overall process, while any streams enriched in linear form but which can be used for other purposes are either removed from the process of the invention or co-exist with the branched-enriched streams. Furthermore, stage (a) (or stage (A), when producing modified primary OXO alcohols) of the process of the present invention suitably comprises the use of at least one selected from the group having a minimum pore size at least larger than that required for the selective adsorption of linear acyclic hydrocarbons. Porous media having a pore size of no more than about 20 angstroms, more preferably no more than about 10 angstroms.

When the hydrocarbon feed comprises more than about 10% paraffins and is constantly at a higher level, such as from about 11% to 90% paraffins or more, it is preferred that the process of the present invention comprises an additional stream that is rich in branching at least Step (b) of partial dehydrogenation. Dehydrogenation can be carried out using a variety of known catalysts and conditions.

When preparing modified alkylbenzenes, regardless of the type of feed, the process of the present invention preferably comprises (c) passing through one or two of the aforementioned steps (optionally adsorption with a dehydrogenation step) in the presence of an alkylation catalyst. Separation step, provided that the branch-rich stream ultimately comprises generally at least about 5%, more usually at least about 15%, typically 5%-90% or more olefins) the produced branch-rich stream is combined with a olefin selected from benzene , toluene and aromatic hydrocarbons of their mixtures. The preferred alkylation step herein has a low internal isomer selectivity of from 0 to no more than about 40, preferably no more than about 20, and is more fully described and defined elsewhere herein. Alkylation with such a low alkylation selectivity in the literature of modified alkylbenzene production is believed to be novel in itself.

The preferred method here also preferably satisfies at least one, more preferably two, of the following requirements: first, the stage (a) device includes one, two or more than two types of equipment and at least two of the beds, At least one of said beds comprises a porous medium of different composition than the other of said beds to enhance the ability to retain methyl-branched acyclic aliphatic hydrocarbons. For example, zeolites having pore sizes in excess of about 5 Angstroms to no greater than 7 Angstroms are particularly preferred. Second, when producing modified alkylbenzenes, said step (c) has an internal isomer selectivity of from 0 to no more than about 40, preferably lower (as further defined hereinafter).

The various methods preferred herein operate in a manner contrary to and inconsistent with conventional practice for the preparation of alkylbenzenesulfonate surfactants (collecting the linear material for further processing and discharging most of the branched material). Furthermore, in order to achieve this modification, we found it necessary to use the unconventional interconnection of the adsorptive separation operation further described and illustrated in this specification.

Also in various preferred methods herein, said simulated moving bed adsorption separation unit in said stage (a) comprises two of said devices instead of one. The amount of equipment employed and its configuration is of considerable importance in accomplishing the production of the preferred compositions of the present invention and in enhancing the particular type of branching in the hydrocarbon stream.

Additionally, in certain preferred processes having two of said beds, each comprising said porous media of a number of different compositions, each of said beds is controlled by one of said devices, and each of said devices has a minimum of 8 A port (as defined in US 2,985,589) to achieve simulated movement of the porous media in the bed. Also preferred is a distribution of vertical positions where each of said beds is divided into at least 8 sub-beds (see Figure 1 in US 2,985,589). It is also preferred that stage (a) uses all porous media in the bed instead of clathrate compounds.

When producing modified alkylbenzenes, the methods herein may have one or more steps following the alkylation step. These steps may include the additional step (d) of sulfonating the product of step (c). Sulfonation may be followed by an additional step (e) of neutralizing the product of step (d). These steps may be followed by (f) of mixing the product of step (d) or (e) with one or more cleaning product additive materials, whereby a cleaning product is produced.

The present invention also includes modified alkylbenzenes prepared by any of the methods herein; and modified alkylbenzenes prepared by any of the methods herein, in the form of any known salts such as sodium salts, potassium salts, ammonium salts , modified alkylbenzene sulfonic acid or modified alkylbenzene sulfonate surfactants in the form of substituted ammonium salts, etc.; and household cleaning products prepared by any of the methods herein.

Likewise, when anionic surfactants are prepared from the modified primary OXO alcohols described herein, the invention includes all salt forms of the above-specified surfactants.

Embodiments of cleaning products herein (whether incorporating modified alkylbenzene sulfonates and/or incorporating any of the surfactants derived from the modified primary OXO alcohols described herein) include laundry detergents, dishwashing Detergents, hard surface cleaners, etc. In these embodiments, the content of the modified surfactant prepared by the method of the present invention is from about 0.0001% to about 99.9%, usually from about 1% to about 50%, and the composition further includes from about 0.1% to about 99.9%, typically from about 1% to about 90%, of various cleaning product additive materials such as cosurfactants, builders, enzymes, bleaches, bleach boosters, activators or catalysts, and the like.

The present invention also has an alternative adsorptive separation step using a paraffin feed (in which two specific configurations are nearly identical to stage (a) described here for the production of modified alkylbenzenes, followed by other steps than step (c) to obtain a variety of useful cleansing surfactants) embodiments. These alternative step (c) alkylation steps may include at least one step selected from the group consisting of dehydrogenation, chlorination, sulfoxidation to C8-C20 alcohols and oxidation to C8-C20 carboxylic acids or salts thereof, optionally This is followed by one of the following steps: glucosamidation (glucosamidation), conversion to a non-sugar-derived amide surfactant (such as monoethanolamide surfactant or any such amide without a glucose moiety) and sulfonation (conversion to an ester ). Other alternative embodiments employ a hydrocarbon feed comprising 20% or more methyl-branched olefins; also the process has a specially configured stage (a) adsorption separation step. Subsequent steps may include an alkylation step with benzene or toluene, optionally followed by a sulfonation step; an alkylation step with phenol, followed by an alkoxylation, sulfation, sulfonation step, or a variety thereof at least one step in combination; carbonylation to an alcohol, optionally followed by at least one of the following steps: alkoxylation, glycosylation, sulfation, phosphation steps or various combinations thereof; sulfonation; cyclo Oxidation; Hydrobromination followed by an amination step and oxidation to amine oxide; and Phosphorylation.

The invention also includes surfactants prepared by these methods and cleaning products prepared by these methods. The present invention also encompasses particularly useful embodiments wherein the adsorptive separation of stage (a) comprises at least one separation step using organometallic grafted mordenite, such as tin grafted mordenite. The present invention also includes a process for the use of grafted mordenite for the production of detersive surfactants and any corresponding surfactant and lifestyle products prepared by using these special porous media in any of the above processes.

The invention has many other important embodiments and branches. The present invention thus includes a process comprising: (A) a stage of at least partial separation of a hydrocarbon feed comprising branched aliphatic hydrocarbons, more specifically paraffins having from about 8 to about 20 carbon atoms such that which is separated into at least one branched-rich stream containing an increased proportion of branched acyclic hydrocarbons relative to said hydrocarbon feed, and optionally one or more of:

- a linear-rich stream containing an increased proportion of linear aliphatic hydrocarbons relative to said hydrocarbon feed; and

- an exit stream containing cyclic and/or aromatic and/or ethyl or higher branched hydrocarbons; wherein said stage (A) comprises:

- providing said hydrocarbon feed; and

- separating said feed into said stream using porous media adsorptive separation;

Described stage (A) adopts the imitation moving bed adsorption separation device, and this equipment comprises following two kinds:

- at least one bed loaded with said porous media; and

- means in said bed to simulate the movement of porous media countercurrent to the hydrocarbon flow; followed by further stages (B), (C) and (D) (any of them having one or more steps):

(B)(i) at least partially dehydrogenate the branched stream rich in stage (A) thereby forming a branched olefins-rich stream containing monoenes (optionally large proportions, up to 80% or more paraffins can be mixed with impurities such as diene and/or aromatic impurities), optionally followed by one or more of (ii) treating the branched olefin-rich stream to reduce the content of diene impurities therein and (iii) treating the branched-rich stream olefins stream to reduce the content of aromatic impurities therein; (C) optionally employing known adsorbents or porous media by adsorptive separation methods, at least partially concentrating said monomers in said branched olefin-rich stream of stage (B) alkenes, provided that the adsorbent or porous media is different from that of stage (A) and is suitable for olefin/paraffin separation (such as copper-treated or silver-treated zeolites X or Y), optionally with simultaneous recycling of paraffins to said dehydrogenation stage (B); and

(D) reacting said branched olefin-rich stream produced in stage (B) or optionally further concentrated in stage (C) with carbon monoxide and hydrogen in the presence of an OXO catalyst, thereby forming a modified mono grade OXO alcohol.

In the description of the methods herein, the term "stage" refers to a collective combination of one or more process steps that can be regarded as the same. For example (A) is an adsorptive separation stage, essentially a modified MOLEX® stage registered by UOP Corp., here unconventionally configured to increase (rather than decrease as normal) the branching content of hydrocarbons. Auxiliary steps such as distillation, addition while cleaning the adsorbent with lower boiling hydrocarbons or removal steps etc. (all well known in the art) may optionally be included as part of the same stage. (B) is a dehydrogenation stage comprising at least a dehydrogenation step but generally other optional steps such as those specifically described above. The basic process technology for (B) may be UOP Corp. registered as PACOL® method. (C) is basically the regular OLEX_ stage (also provided by UOP Corp.). (D) is preferably an OXO stage of this type known in the art as "one-step low pressure OXO" and also well known in the art. As with the other steps of the process, stage (D) may be supplemented by other optional steps, such as catalyst removal and the like. Unless otherwise stated, it is convention here to use capital letters (A, B, C...) when referring to stages of embodiments of the process of the invention, wherein the process comprises the preparation of a modified primary OXO alcohol.

Surfactants derived from these new modified primary OXO alcohols and the aforementioned alkylbenzenes have distinct advantages such as greater solubility for a given chain length/number of carbons (from increasingly popular low-temperature washes). viewing is important); and an unexpectedly high dissolution rate when added to detergent granules. Thus OXO alcohols and alkylbenzenes themselves are also used in the preparation of cleaning compositions such as heavy duty laundry detergents, dishwashing liquids and the like. All percentages, ratios and proportions herein are by weight unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise indicated. All cited documents are hereby incorporated by reference in relevant part.

Detailed description of the invention

In one embodiment, the present invention is directed to a process for the preparation of modified alkylbenzene sulfonate surfactants from hydrocarbon feedstocks. The terms "feed" and/or "feedstock" are used synonymously herein to refer to any hydrocarbon that may be used as a feedstock in the process of the present invention. In contrast, the term "stream" is generally used to denote hydrocarbons that have undergone at least one process step. Generally, the hydrocarbon feed here contains useful proportions of acyclic aliphatic hydrocarbons (whether olefins or paraffins, or may include mixtures of such olefins and paraffins). The feedstock also typically includes varying amounts of cyclic and/or aromatic hydrocarbon impurities (as found in kerosene, brown carbon/diesel (middle cut) hydrocarbon cuts). Olefins and paraffins usually exist in both branched and linear forms in the feedstock. Furthermore, in general, branching patterns in the feedstock may or may not meet the requirements of the invention. The purpose of the present invention to provide cleaning products differs significantly from, for example, gasoline production (where highly polymethylated branched hydrocarbons are required for octane enhancement). The present invention provides various methods for the separation of hydrocarbon feedstocks in particularly desirable forms for cleaning products, and their incorporation into surfactants (especially certain modified alkylbenzene sulfonates and/or based on modified Surfactants for primary OXO alcohols) and cleaning products and various useful surfactant intermediates for such products.

The term "modified" used in connection with any product of the process of the present invention means that the product contains a very specific type of branching and deviates surprisingly from a linear structure (which is now commonly preferred and used in surfactants for cleaning products). ). The term "modified" is also used to distinguish the products herein from conventional hyperbranched cleansing surfactant structures such as those found in tetrapropenylphenyliodate, and from all other conventional branched Structures such as "two-tailed" or "Guerbet" or branched structures derived from 3-hydroxybutyraldehyde are distinguished.

In general the hydrocarbon feed here can be varied, but typically includes various methyl-branches such as monomethyl, dimethyl (including gem-dimethyl), trimethyl, polymethyl, ethyl and Higher alkyl branch. The hydrocarbon feed may contain quaternary carbon atoms. However, when the process includes the alkylation step described hereinafter, the tolerance of quaternary carbon atoms in the feed is too strong. In embodiments of the invention having an OXO process stage and no alkylation stage, it is preferred that the feed therein be substantially free of quaternary carbon atoms. Desirable components for the purposes of the present invention include monomethyl-branches, dimethyl-branches (except gem-dimethyl-branches) and to some extent (especially when the number of carbon atoms exceeds about 14 o'clock) part of the trimethyl-branch. The hydrocarbon feed also includes various useful proportions such as 5% to 40% or more of acyclic hydrocarbons (typically having from about 9 to about 20 carbon atoms, depending on the cleaning product surfactant prepared with the resulting modified surfactant or the desired type of cleaning product). More preferably, the acyclic aliphatic hydrocarbon of the feedstock when preparing the modified alkylbenzenes and modified alkylbenzene sulfonates comprises from about 10 to about 16, more preferably from about 11 to about 14 carbon atoms.

The process of the present invention includes a specific adsorption separation stage. In addition, an alkylation stage is also necessary for the preparation of modified alkylbenzenes and alkylbenzene sulfonates. When the feedstock is a paraffin, embodiments of the process of the invention typically and preferably also include a dehydrogenation stage interspersed between the adsorptive separation and the alkylation sequence, or, when producing modified primary OXO alcohols, in the so-called Between the SOR 4/5 or SOR 5/7 adsorption separation type and OXO process stages. In general, the alkylation or OXO stage can be followed by various other steps such as sulfonation, usually followed by neutralization and formulation into household cleaning products by mixing, agglomeration, coagulation, spray drying, etc. Also in general any phase can have more than one step, provided that it includes at least one minimum step.

Stage (a), i.e. adsorptive separation, comprises at least partial separation of a hydrocarbon feed selected from olefin feeds, paraffin feeds and mixed olefin/paraffin feeds to comprise at least one branch relative to said hydrocarbon feed The proportion of acyclic hydrocarbons (especially the various types mentioned above, especially methyl-branched paraffins or methyl-branched monoolefins) increased (such as relative to the feed by more than at least about 50%, more preferably At least more than about 100%, usually three times, four times or more, the absolute weight percentage is at least about 10% by weight, usually at least 20%, more preferably 30% to about 90% or more ), and optionally one or more of the following: comprising an increased proportion of linear acyclic aliphatic hydrocarbons relative to the hydrocarbon feed (e.g., greater than at least about 50%, more relative to Preferably at least more than about 100%, usually three times, four times or more, absolutely at least about 10% (by weight), usually at least 20%, more preferably 30% to about 90% or more) of a linear-rich stream; and an effluent stream comprising cyclic and/or aromatic hydrocarbons or other various impurities such as gem-dimethyl hydrocarbons, ethyl-branched hydrocarbons or higher-branched hydrocarbons.

The various other streams present in the process of the invention may vary in composition. These streams include effluent streams in which cyclic and/or aromatic undesirable various components from the feed are generally present in excess of their amounts in the feed; have various compositions depending on the method of attachment of the various fractions, etc. circular logistics. Various known methods can be used here, such as the method of US 5,012,021 or US 4,520,214 (both are incorporated herein by reference), using selective catalysts to convert various impurities (such as certain diolefins) into a Olefins. Various other methods that may optionally be incorporated herein to selectively remove aromatic by-products formed during the dehydrogenation of paraffins include those of US 5,300,715 and US 5,276,231, involving the use of one or more aromatic removal zones (removal zones) and/or various extractants for aromatics, such as sulfolane and/or ethylenediamine.

In more detail, the adsorptive separation stage or part of the process of the present invention for increasing the branched hydrocarbon content in the feed has one or more steps comprising at least one step selected from the step of providing a suitable hydrocarbon feed and at least one step selected from the step of using porous media The adsorption separation step carried out, the clathrate step carried out with a clathrate compound selected from urea, thiourea, and alternatively a clathrate amide, and various combinations thereof. More preferably, when various combinations are used, at least one step is an adsorption separation step using a porous medium of a large pore type (to be described in more detail hereinafter). Stage (a) (or stage (A), when used to make modified primary OXO alcohols) employs a simulated moving bed adsorption separation unit known in the art (see in particular US 2,985,589, incorporated herein in its entirety) ) comprising at least one bed carrying said porous medium or clathrate compound (see, for example, US 2,985,589 Figure 1 and related specifications) and said porous medium or clathrate compound used in said bed to simulate countercurrent flow with a hydrocarbon stream. Devices for compound movement (see in particular US 2,985,589 Figure 2 and the associated description, or the various variants that are used in the industry today to produce shaped alkylbenzene sulfonates). The devices mentioned are usually highly specialized designed rotary valves. In general, the type of valve available here is the same type currently used for linear alkylbenzenes. Various adsorption separation conditions such as pressure, temperature and time used in the art can be employed. See for example US 2,985,589.

What is particularly unusual and novel about the process of the present invention is that the moving bed adsorption separation step simulated here is minimally used to extract a mainly branch-rich stream, i.e. exactly the same as that used for linear alkylbenzene sulfonate surfactants. The practice of production is the opposite. This major difference is also related to changing the bed composition so that it contains a different porous media than the 4-5 Angstrom zeolites typically produced with linear alkylbenzenes and reconfiguring the process equipment (particularly the bed and the equipment) so that Make it relevant to connect with the relevant process steps. More specifically, these devices are constructed so that branched streams are passed through the overall process, while any streams enriched in linear form but which can be used for other purposes are either removed from the process of the invention or co-exist with the branched-enriched streams.

When the hydrocarbon feed comprises less than about 5% olefins, the process of the present invention preferably includes an additional step (b) of at least partial dehydrogenation of the product of stage (a), or step (B) (when producing improved Sexual primary OXO alcohol). Dehydrogenation can be carried out using any known dehydrogenation catalyst such as the De-H series from UOP and is further described hereafter. The various dehydrogenation reaction conditions are similar to those employed today in the production of linear alkylbenzene sulfonates.

When preparing modified alkylbenzenes, no matter what type of raw material is processed, the process of the present invention preferably comprises the product of stage (a) (or when stage (b) also exists in the above step, stage (a) together with The product of the latter (b)) is reacted with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst. As more fully described and defined elsewhere herein, preferred alkylation steps herein have a low internal isomerism of from 0 to about 40, preferably no more than about 20, more preferably no more than about 10 selective. Such a low selectivity for internal isomers is believed to be novel in itself.

In one mode, the alkylation step here is carried out in the presence of excess paraffins which are then recovered and recycled to the dehydrogenator. In another mode, the alkylation step is carried out in the presence of a 5-fold to 10-fold excess of arene. Various combinations of these modes are also possible.

Note that when the final branch-rich stream, the product of stage (a), has a suitable olefin content (e.g., over about 5% total olefins), this stream can go directly to the alkylation step (c) and can then be The recovered paraffins are recycled to the dehydrogenation reactor for at least partial conversion to olefins. See Figures 5, 6, 7 for example.

Quite importantly for the present invention, the preferred process here also preferably meets at least one, more preferably both of the following requirements: First, the stage (a) unit (or when producing modified primary OXO alcohols Stage (A) means) comprising one, two or more of said devices (such as the above-mentioned rotary valve or any equivalent means) and at least two of said beds, at least one of said beds comprising a different The composition of the bed to enhance the ability of the porous media to retain methyl-branched acyclic aliphatic hydrocarbons. For example, zeolites or other porous media such as certain silicoaluminophosphates with pore sizes at least in excess of those used in conventional linear alkylbenzene production and up to about 20 angstroms, more preferably up to about 10 angstroms, and even more preferably up to about 7 angstroms Or MobilMCM-type materials are also suitable here, provided that the pore size range is as described above. When using porous media with pore sizes in excess of about 7 Angstroms, it is often highly desirable to "turn down" the pore openings (eg, by grafting alkyltins at the pore openings). See EP 559,510A, incorporated herein in its entirety. Second, when preparing modified alkylbenzenes, said step (c) has an internal isomer selection of from 0 to no more than about 40, preferably lower (as described above and defined in further detail hereinafter) sex.

In another preferred process, at least one of said beds comprises porous media conventionally used for the production of paraalkylbenzene; said bed is connected to said process in the following manner: at least partly increased methyl-branched acyclic aliphatic The proportion of hydrocarbons entering step (c) of the process, and at least partially reducing the proportion of linear acyclic aliphatic hydrocarbons entering step (c) of the process, said linear acyclic aliphatic hydrocarbons entering step (c) in stage (a) at least as discharge stream. In other words, the preferred process herein operates in a manner contrary to and inconsistent with conventional practice for the preparation of alkylbenzenesulfonate surfactants (drawing off the branched material and collecting the linear material for further processing). Furthermore, in order to achieve this modification, we found it necessary to use the unconventional interconnection of the adsorptive separation operation already outlined and as further illustrated in the figures herein.

It is also of considerable importance in the preferred process here that the simulated moving bed adsorption separation unit in stage (a) (or stage (A), when producing modified primary OXO alcohols) comprises two and Not one of said devices, or a single device that can simulate the movement of said porous media in at least two separate beds. In other words, for all of the preferred methods herein, a single device such as that described in US 2,985,589 would not suffice. The amount of equipment and its configuration are of considerable importance to accomplish the production of the preferred compositions of the present invention. Thus, in a hypothesis unknown in the art, further purification of linear hydrocarbons can be accomplished by two devices and two beds connected in series. The highly linear adsorbate in the first stage can enter the second stage of adsorption separation process for further purification. Such a structure is outside the scope of the present invention in view of its incorrect linkage at various stages leading to increased linearity and purity of the hydrocarbon. As already mentioned, the method of the present invention involves passing the branch streams through various steps or stages, requiring the connection of various devices consistent with the objective. This adds a special type of branching in the hydrocarbon stream here.

It is also of considerable importance in the preferred method here that there are two said beds, one of which comprises said porous media of a different composition, each said bed being controlled by one said device, and each said device A minimum of 8 ports is required to simulate the movement of the porous media in the bed. Each of said beds is also preferably divided into a vertical distribution of at least eight sub-beds. It is also preferred that stage (a) uses entirely porous media in the bed. Thus, the present invention can use conventional beds and equipment of the general type described in US 2,985,589, but their number and connection to the process of the present invention are novel and unprecedented in an alkylbenzenesulfonate production facility.

Also, to better illustrate what has been described in certain embodiments of the preferred process herein, the enriched linear stream is present in stage (a), and stage (a) consists of: (a-i) passing one of said simulated moving bed devices adsorptively separates said hydrocarbon feedstock into said linear-enriched stream and an intermediate stream enriched in branches, and withdraws said linear-enriched stream as required by said process objectives; followed by (a -ii) adsorptive separation of said branch-rich intermediate stream to include a ratio of acyclic aliphatic hydrocarbon branches (in particular methyl-branches) relative to said linear-rich stream by means of another said simulated moving bed Said branch-rich stream is increased and an exit stream comprising at least an increased proportion of cyclic and/or aromatic hydrocarbons relative to said branch-rich stream.

The effluent stream in said step (a-ii) may further comprise undesired branched hydrocarbons selected from the group consisting of gem-dimethyl branched hydrocarbons, ethyl branched hydrocarbons, and branched hydrocarbons higher than ethyl; and wherein The acyclic aliphatic hydrocarbons of the branch-enriched intermediate stream and the branch-enriched stream include a reduced proportion of the gem-dimethyl branched hydrocarbons, ethyl-branched hydrocarbons and ratio ethyl branched hydrocarbons relative to the hydrocarbon feed. higher branched hydrocarbons. Depending on the tolerance of this different component in the intermediate branch-rich stream, ethyl branched hydrocarbons are much more acceptable than gem dimethyl, cyclic and aromatic components. In general, minimal "increase in proportion", "decrease in proportion" or "enrichment" of any component in any step herein corresponds to any increase in proportion that can be practically used for the aforementioned purposes of the present invention ( enrichment) or decrease. These amounts will be specified throughout the specification.

Simultaneously in described method, can obtain described each stream composition by selecting following material as described porous medium: in described step (a-i), be selected from the composition of 4-5 angstrom pore size zeolite and in described The composition of the porous media selected in step (a-ii) having a pore size at least greater than about the largest pore size of the zeolite of said step (a-i).

In another preferred embodiment, stage (a) comprises: (a-i) adsorptive separation of said hydrocarbon feed into a rich mixture comprising linear- and branched (e.g. desired types as described above) acyclic aliphatic hydrocarbons. an acyclic aliphatic hydrocarbon-containing stream and a first effluent stream comprising at least an increased proportion of cyclic and/or aromatic hydrocarbons relative to said hydrocarbon feed, followed by (a-ii) said acyclic aliphatic-rich The hydrocarbon stream is adsorbed and separated into the branch-rich stream and the linear-rich stream; wherein the adsorptive separation is carried out by using the simulated moving bed adsorptive separation device. Here, unless otherwise stated, "branched stream" refers to the final stream of stage or step (a); other modifiers such as "intermediate" will be fixed in advance in the name denoting this stream, although the branched hydrocarbons get enrichment, but still requires further treatment before passing from the adsorptive separation stage of the process to another stage. It should also be mentioned that stage (a), ie the adsorptive separation stage, can freely comprise other customary optional steps such as distillation, provided that the adsorptive separation is carried out. Therefore, current industrial ^MOLEX® equipment usually also includes distillation in this stage and can be used here.

The present invention also includes a process wherein said first effluent stream in said step (a-i) further comprises an undesired group selected from gem-dimethyl branched hydrocarbons, ethyl-branched hydrocarbons and higher than ethyl branched hydrocarbons of branched hydrocarbons; and wherein said acyclic aliphatic hydrocarbon-rich stream and said branched-rich stream each comprise a reduced proportion of said gem-dimethyl group relative to said hydrocarbon feed Branched hydrocarbons, ethyl-branched hydrocarbons, and branched hydrocarbons higher than ethyl. In these embodiments, the composition of each stream can be obtained by selecting the following materials as the porous media: in the step (a-ii) selected from the composition of 4-5 angstrom pore size zeolites and in the step The composition of (a-i) is selected from porous media having a pore size at least greater than about the maximum pore size (up to about 10 Angstroms) of the zeolite of step (a-ii).

More generally, the present invention relates to a process wherein stage (a) comprises the use of at least one porous medium selected from the group having a minimum pore size larger than that required for the selective adsorption of linear acyclic hydrocarbons, said pore size not exceeding About 20 Angstroms.

As mentioned above, preferred methods herein include wherein said alkylation step (c) has an internal isomer selectivity of 0-20; An alkylation catalyst with consistent isomer selectivity, and wherein said alkylation catalyst is selected from the group consisting of at least partially acidic mordenite and at least partially acidic beta zeolite. Preferred alkylation catalysts include H-mordenite and H-beta mordenite, more preferably at least partially dealuminated H-mordenite.

In terms of producing modified alkylbenzenes and modified alkylbenzene sulfonates, the present invention also preferably includes a process wherein the hydrocarbon feed comprises at least about 10% methyl-branched paraffins of molecular weight is at least about 128 and not more than about 282; said process having said dehydrogenation step (b). More preferably in this embodiment, said hydrocarbon feed comprises at least about 20% methyl-branched paraffins having a molecular weight of at least about 128 and not more than about 226; said process has said dehydrogenation step (b ) and alkylation step (c); the present invention also preferably includes a process wherein the hydrocarbon feed comprises at least about 10% methyl-branched olefins having a molecular weight of at least about 126 and not more than about 280. More preferably in this embodiment, the hydrocarbon feed comprises at least about 50% methyl-branched olefins having a molecular weight of at least about 126 and not more than about 224; the process is devoid of the dehydrogenation step (b).

For corresponding processes to prepare modified primary OXO alcohols, the above range can be extended to some extent, keeping the total number of carbon atoms at about _C20 or higher. More preferably, the molecular weight of paraffins with the above-mentioned upper limit of 226 is increased to about 254, and the molecular weight of olefins with the above-mentioned upper limit of 224 is increased to about 252.

Most usefully for detergent manufacturers, the hydrocarbon feed or feedstock here can be an adsorption separation raffinate or waste stream from a linear alkylbenzene production process.

The methods herein may have one or more steps after the alkylation step. These steps may include (d) a further step of sulfonating the product of step (c). The sulfonation step may be followed by a further step of (e) neutralizing the product of step (d). These steps may be followed by the step of (f) mixing the product of step (d) or (e) with one or more cleaning product additive materials; thereby producing a cleaning product.

The process here therefore includes highly preferred embodiments having all the other steps of: (d) sulfonating the modified alkylbenzene product of step (c); (e) neutralizing the modified alkylbenzene of step (d) and (f) combining the modified alkylbenzene sulfonic acid or modified alkylbenzene sulfonate surfactant product of step (d) or (e) with one or more cleaning product additive materials The mixing is carried out whereby a cleaning product is formed. In one such embodiment, the modified alkylbenzene of the product of step (c) is blended with linear alkylbenzene prepared by conventional methods prior to performing the sulfonation step. In another such embodiment, the modified alkylbenzene sulfonate salt of the product of step (d) is combined with linear alkylbenzene sulfonic acid prepared by conventional methods in any step after said sulfonation step Salt is blended. In these blended embodiments, the preferred process has a ratio of modified alkylbenzene to linear alkylbenzene of from about 1:100 to about 100:1. When more linear product is desired, the preferred ratio is from about 10:90 to about 50:50. When more branched products are desired, the preferred ratio is from about 90:10 to about 51:49.

The present invention also includes modified alkylbenzenes prepared by the various methods herein; and modified alkylbenzenes prepared by the various methods herein, in any known salt form such as sodium salt, potassium salt, ammonium salt, substituted ammonium Modified alkylbenzene sulfonic acids or modified alkylbenzene sulfonate surfactants in the form of salts and the like; and household cleaning products prepared by the various methods herein.

Cleaning product embodiments herein include laundry detergents, dish detergents, hard surface cleaners, and the like. In these embodiments, the content of the modified alkylbenzene sulfonate prepared by the method of the present invention, or the surfactant derived from the modified primary OXO alcohol etc. herein is about 0.0001% to about 99.9%, Typically from about 1% to about 50%, and the composition also includes from about 0.1% to about 99.9%, typically from about 1% to about 50%, of various cleaning product additive materials such as co-surfactants, builders, enzymes , bleach, bleach accelerator, activator or catalyst, etc.

Preferred household cleaning products made by these methods suitably comprise from about 1% to about 50% of said modified surfactants and from about 0.0001% to about 99% of a cleaning product additive material selected from the group consisting of enzymes, non-phosphates, co- Lotions, polymers, activated bleaches, catalyzed bleaches, photobleaches and mixtures thereof. Alternative method implementation

The present invention has various alternative embodiments in which two specifically configured adsorption separation steps are followed by various other steps to obtain useful cleansing surfactants. Accordingly, a process is encompassed herein which comprises: (I) separating a hydrocarbon feed into a branch-rich branch comprising (more preferably consisting essentially of) at least about 85% saturated acyclic aliphatic hydrocarbons having a carbon content of from about C8 to about C20 A stream of hydrocarbons that is rich in branched hydrocarbons comprising at least about 10% paraffins having methyl branching distributed among the paraffins such that the paraffin molecules have from 0 to no more than about 3 said methyl branches and said branches are located within said paraffin in such an amount that at least about 90% of said branches occupy positions other than those forming geminal dimethyl and/or quaternary groups; wherein said separation Carry out by including at least two adsorption separation steps using a simulated moving bed adsorption separation device and at least two porous media with different pore sizes; Conversion of the stream of branched hydrocarbons to surfactants: dehydrogenation, chlorination, sulfoxidation, oxidation to C8-C20 alcohols and oxidation to C8-C20 carboxylic acids or their salts, optionally followed by a step selected from: Glucoamidation (conversion to non-carbohydrate derived amide surfactants) and sulfonation (conversion to esters).

In addition, as an alternative embodiment, a method is also included herein, which includes: (I) separating the hydrocarbon feed into a mixture comprising (preferably mainly comprising) olefinic acyclic aliphatic hydrocarbons having a carbon content of about C8-C20 An olefin-branched hydrocarbon-rich stream comprising a total of at least about 10% of said olefins and their saturated homologues having methyl branches, or mixtures thereof with saturated homologues, said branched hydrocarbon-rich streams distributed in said mixture such that any of said acyclic aliphatic hydrocarbon molecules have from 0 to no more than about 3 said methyl branches, and said branches are present in said acyclic aliphatic hydrocarbon molecules in such an amount that at least about 90% of the branches occupy positions other than the formation of gem-dimethyl groups; wherein the separation is by means of adsorption separation comprising at least two simulated moving bed adsorption separation devices and at least two porous media with different pore sizes and (II) converting said olefinically branched hydrocarbon-rich stream into surfactants by at least one other step selected from the following steps: an alkylation step with benzene or toluene, optionally followed by is a sulfonation step; an alkylation step with phenol, followed by at least one of an alkoxylation, sulfation, sulfonation step or various combinations thereof; carbonylation, optionally followed by at least one The following steps: alkoxylation, alkoxylation combined with oxidation, glycosylation, sulfation, phosphating steps or various combinations thereof; sulfonation; epoxidation; hydrobromination followed by amination and oxidation to amine oxides; and phosphorylation.

In view of the various alternative methods involved, the present invention also includes various surfactants prepared by these methods and various cleaning products prepared by these methods.

Various aspects of the invention are now discussed and illustrated in more detail. Modified alkylbenzene and alkylbenzene sulfonate products

As mentioned in the Summary, the present invention includes a process for the preparation of modified alkylbenzene sulfonate surfactants suitable for use in various cleaning products such as laundry detergents, hard surface cleaners, dish detergents, and the like.

The terms "modified alkylbenzene sulfonate surfactant" and "modified alkylbenzene" refer to the products of the various processes herein. The term "modified" for the novel alkylbenzene sulfonate surfactants or novel alkylbenzenes (MABs) is intended to mean that the product of the process of the present invention is compositionally different from that found in all commercial household cleaning compositions. Alkylbenzenesulfonate surfactants used. More specifically, the compositions of the present invention are compositionally distinct from so-called "ABS" or poorly biodegradable alkylbenzene sulfonates, and from so-called "LAS" or linear alkylbenzene sulfonate surface active agent. The various LAS surfactants that are currently conventional are obtained by several industrial processes including those relying on HF-catalyzed or aluminum chloride-catalyzed alkylation of benzene. Various other commercial LAS surfactants include LAS prepared by the ^DETAL method. The herein preferred alkylbenzene sulfonate surfactants prepared using the herein preferred low-internal isomer selective alkylation step are also compositionally distinct from those obtained by employing fluorinated zeolite catalyst systems (believed to also include Fluorinated mordenite) is a surfactant prepared by alkylation of linear olefins. Without being bound by theory, we believe that the modified alkylbenzene sulfonate surfactants herein are uniquely slightly branched. They usually contain large amounts of isomers and/or homologues. This large number of species (usually tens or even large numbers) is usually accompanied by a higher total content of 2-phenyl isomers, the content of 2-phenyl isomers is at least 25%, usually 50% or even 70% % or higher. In addition, the modified alkylbenzene sulfonate products herein differ from known alkylbenzene sulfonate surfactants in various physical properties, such as having improved surfactant efficiency and less occurrence of Phase separation of the endo isomer from the solution, especially in the presence of water hardness. Feeds and streams of the process of the invention

The term "feed" is used here to refer to material which has not been processed by the process of the invention. However, the feed term may also be used when an optional step in the process of the invention (such as adsorptive separation on 5 Angstrom Ca-zeolite) is applied to such a material, provided that such treatment is performed in the process of the invention implementation before the first major steps are taken.

The term "stream" is used herein to refer to material that has undergone at least one step of the process of the invention.

As used herein, unless more specifically stated, the term "branch-enriched stream" means any processed hydrocarbon fraction containing at least lesser amounts of:

(i) Relatively speaking, an increase of at least about 10%, preferably at least 100% (i.e. doubling), more preferably three-fold, four-fold or Higher branched acyclic C8-about C20 hydrocarbons; or

(ii) Absolutely, when the process produces modified alkylbenzenes or modified alkylbenzene sulfonates, at least about 5%, preferably 10% or more branched acyclic C8 to about C20 Hydrocarbons, more preferably about C10 to about C14 hydrocarbons.

The branched hydrocarbons mentioned may be olefins, paraffins or mixed olefins/paraffins in any ratio (unless more specifically stated). (Some preferred methods involve the production of modified primary OXO alcohols, as shown in Figure 9 and from a higher starting point with a paraffinic feed, more generally as variations of the process can employ an olefinic feed). The branch is preferably a monomethyl branch or an isolated (non-geminal) dimethyl branch.

Unless more specifically stated, the term "linear-rich stream" as used herein refers to any processed hydrocarbon fraction containing a higher Normal (n-) acyclic hydrocarbon in weight percent.

More specifically, a "linear-enriched" stream refers to any processed hydrocarbon fraction containing at least minor amounts of:

(iii) Relatively speaking, an increase of at least about 10%, preferably at least 100% (i.e. doubling), more preferably three-fold, four-fold or Higher linear acyclic C8-about C20 hydrocarbons; or

(iv) Absolutely at least about 5%, preferably 10% or more linear acyclic C8 to about C20 hydrocarbons.

The linear hydrocarbons mentioned may be olefins, paraffins or mixed olefins/paraffins in any ratio (unless more specifically stated).

Various modifiers such as "intermediate" when used with a branch-enriched stream are used to refer to the so-called branch-enriched stream which has not completely passed through the adsorptive separation stage (a) of the process of the invention. Other modifiers such as "olefinic" or "paraffinic" and the like may be used to refer to whether the stream contains predominantly olefins or paraffins.

The various feeds and streams in the process of the present invention according to embodiments involving alkylation and according to involving OXO reactions (or both) are further shown in the table below. Numbers in the leftmost column refer to the feeds and streams in Figures 1-18. logistics Logistics type/name Exemplary source (feed) or composition (stream) main component 1 hydrocarbon feed The brown carbon/kerosene fraction, preferably from light crude oil, is preferably fed as a narrower cut cut (such as 3, 2, 1 or carbon spread or non- Narrow cut fraction of integers) b-paraffins/l-paraffins 2 branch-rich stream (intermediate) Mainly branched chain alkanes; also includes cyclic compounds, aromatic hydrocarbons b-alkanes 3 branch-rich logistics Mainly methyl branched paraffins b-alkanes 4 Branched-rich stream (olefinic) Predominantly methyl branched paraffins; amounts of methyl branched olefins such as up to about 20%; diene impurities may also be present b-alkanes/b-alkenes 5 Modified alkylbenzene Mainly methyl branched alkylbenzenes Modified alkylbenzenes prepared by the process of Figure 1 with an alkylation step 6 linear-rich logistics Mainly linear paraffins l-alkanes 7 Exhaust stream (circularization Cyclic compounds, aromatic hydrocarbons, ethyl and compounds/aromatics) Higher branched alkanes 8 Circular logistics Mainly methyl branched paraffins b-alkanes 9 hydrocarbon feed Brown carbon/kerosene fraction, preferably from light crude oil b-paraffins/l-paraffins 10 branch-rich stream (intermediate) Mainly methyl branched and linear paraffins b-paraffins/l-paraffins 11 branch-rich logistics Mainly methyl branched alkanes b-alkanes 12 Branched-rich stream (olefinic) Predominantly methyl branched paraffins; amounts of methyl branched olefins such as up to about 20% b-alkanes/b-alkenes 13 Modified alkylbenzene Mainly methyl branched alkylbenzenes Modified alkylbenzenes prepared by the process of Figure 2 with an alkylation step 14 Exhaust stream (cyclic compounds/aromatics) Cyclic compounds, aromatics, ethyl- and higher branched alkanes 15 linear-rich logistics Mainly linear paraffins l-alkanes 16 Circular logistics Mainly methyl branched alkanes b-alkanes 17 hydrocarbon feed Brown carbon/kerosene fraction, preferably from light crude oil b-paraffins/l-paraffins 18 branch-rich logistics Mainly methyl branched and linear paraffins b-paraffins/l-paraffins 19 Branched-rich stream (olefinic) Predominantly methyl branched and linear paraffins; must have some linear and methyl branched alkenes b-alkanes/l-alkanes/b-alkenes/l-alkenes 20 Linear and modified alkylbenzenes Mainly methyl branched and linear alkylbenzenes Linear and modified alkylbenzene mixtures prepared by the method of Figure 3 twenty one discharge logistics Cyclic compounds, aromatics, ethyl and higher branched paraffins twenty two Circular logistics Mainly methyl branched and linear paraffins b-alkanes l-alkanes twenty three hydrocarbon feed Mixture of branched alkanes with cyclic compounds and aromatics, derived from conventional LAB equipment effluents such as ^MOLEX_Waste b-alkanes twenty four branch-rich logistics Mainly methyl branched paraffins b-alkanes 25 Branched-rich stream (olefinic) Predominantly methyl branched paraffins; the amount of methyl branched olefins must be e.g. up to about 20% b-alkanes/b-alkenes 26 modified alkylbenzene Mainly methyl branched alkylbenzenes Modified alkylbenzene prepared by the method shown in Figure 4 27 discharge logistics Cyclic compounds, aromatics, ethyl and higher branched paraffins 28 Circular logistics Mainly methyl branched paraffins b-alkanes 29 hydrocarbon feed FT gasoline, advanced cuts; cracking products from bulk alkanes; cracking products from Flexicoker or Fluidcoker b-alkenes/l-alkenes/b-alkanes/l-alkanes 30 branch-rich stream (intermediate) Predominantly methyl branched and linear olefins; often paraffins with some linear and methyl branching b-alkenes/l-alkenes/b-alkanes/l-alkanes 31 branch-rich logistics Predominantly methyl branched olefins and methyl branched paraffins; ratios vary b-Olefins/b-Alkanes 32 Stream rich in branching (olefins) Predominantly methyl branched paraffins; amounts of methyl branched olefins such as up to about 20% b-alkanes/b-alkenes 33 modified alkylbenzene Mainly methyl branched alkylbenzenes Modified alkylbenzene prepared by the method in Figure 5 34 Exhaust stream (cyclic compounds/aromatics) Cyclic compounds, aromatics, ethyl- and higher branched alkanes 35 Linear-rich stream (may include cyclic compounds/aromatics) Mainly linear olefins and linear paraffins l-alkenes/l-paraffins 36 Circular logistics Mainly methyl branched paraffins b-alkanes 37 hydrocarbon feed FT Gasoline, Premium Cut; come b-alkenes/l-alkenes/b- Cracking products of self-loose alkanes; Cracking products from Flexicoker or Fluidcoker Paraffins/l-paraffins 38 branch-rich stream (intermediate) Branched olefins, branched alkanes, cyclic compounds and aromatics b-Olefins/b-Alkanes 39 branch-rich logistics Predominantly methyl branched olefins and methyl branched paraffins; ratios vary b-Olefins/b-Alkanes 40 Branched-rich stream (olefinic) Predominantly methyl branched paraffins; amounts of methyl branched olefins such as up to about 20% b-alkanes/b-alkenes 41 modified alkylbenzene Mainly methyl branched alkylbenzenes Modified alkylbenzene prepared by the method shown in Figure 6 42 linear-rich logistics Mainly linear olefins and linear paraffins l-alkenes/l-paraffins 43 Exhaust stream (cyclic compounds/aromatics) Cyclic compounds, aromatics, ethyl- and higher branched alkanes 44 Circular logistics Mainly methyl branched paraffins b-alkanes 45 hydrocarbon feed FT gasoline, advanced cuts; cracking products from bulk alkanes; cracking products from Flexicoker or Fluidcoker b-alkenes/l-alkenes/b-alkanes/l-alkanes 46 branch-rich logistics Predominantly methyl branched and linear olefins; often paraffins with some linear and methyl branching b-alkenes/l-alkenes/b-alkanes/l-alkanes 47 Branched-rich stream (olefinic) Predominantly linear and methyl branched paraffins; alkenes with some linear and methyl branching b-alkanes/l-alkanes/b-alkenes/l-alkenes 48 Modified alkylbenzene Mainly methyl branched and linear alkylbenzenes Modified alkylbenzene prepared by the method in Figure 7 49 Exhaust stream (cyclic compounds/aromatics) Cyclic compounds, aromatics, ethyl- and higher branched alkanes 50 Circular logistics Mainly methyl branched and linear paraffins b-alkanes l-alkanes 51 crude hydrocarbon feed Paraffins in the kerosene range; 360-500°F b-alkanes (182-277°C), preferably from light paraffin feedstock l-alkanes 52 Lightly cut fractions (not used in the preparation of OXO alcohols or modified LABs) Light cut - eg 360°F to product cut 53 Heavy cut fractions (not used in the preparation of OXO alcohols or modified LABs) Heavy Cut - Cut product from overhead to 530°F 54 Branched-rich stream (olefins) (de-dienes) The amount of predominantly methyl-branched paraffins and methyl-branched olefins is, for example, up to about 20% (essentially free of dienes and/or aromatics) b-alkanes b-alkenes 55 Branched-rich stream (olefins) (de-dienes) Mainly methyl branched alkenes b-olefins 56 Modified primary OXO alcohol Mainly modified primary OXO alcohol and a small amount of paraffin Modified primary OXO alcohol 57 Modified primary OXO alcohols (no recyclable substances) Modified primary OXO alcohol Modified primary OXO alcohol 58 Crude Modified Primary OXO Alcohol Mainly modified primary OXO alcohols and α-, ω-diols and a small amount of paraffins Modified primary OXO alcohol 59 Modified alkylbenzenes and paraffins Mainly modified primary OXO alcohols and up to about 30% modified alkylbenzenes b-paraffin modified alkylbenzene 60 Modified primary OXO alcohols and paraffins Predominantly methyl branched paraffins and up to about 25% modified primary OXO alcohols b-paraffin modified primary OXO alcohol 61 Linear and methyl branched alkenes in paraffins Predominantly linear paraffins and methyl branched paraffins, linear olefins and methyl branched alkenes present up to about 20% (essentially free of dienes and/or aromatics) (linear compounds effectively dilute branched compounds) b-alkanes l-alkanes b-alkenes l-alkenes 62 Linear and methyl branched alkenes Mainly linear olefins and methyl branched olefins b-alkenes l-alkenes 63 Mixture of modified primary OXO alcohols and conventional OXO alcohols Mainly conventional OXO alcohols and modified primary OXO alcohols and a small amount of paraffins Modified primary OXO alcohol Linear OXO alcohol 64 Another mixture of modified primary OXO alcohols and conventional OXO alcohols Mainly conventional OXO alcohols and modified primary OXO alcohols, without a small amount of paraffins Modified primary OXO alcohol Linear OXO alcohol 65 Mixture of modified primary OXO alcohols and conventional OXO alcohols in paraffins Predominantly linear paraffins and methyl branched paraffins and up to about 25% of conventional OXO alcohols (primary OXO alcohol type formed from OXO reactions of linear feedstocks) and modified primary OXO alcohols b-alkanes l-alkanes modified primary OXO alcohols Linear OXO alcohols 66 Mixtures of modified and linear alkylbenzenes in paraffins Predominantly linear and methyl branched paraffins and up to about 30% linear and modified alkylbenzenes b-alkanes l-alkanes modified alkylbenzenes l-alkylbenzenes

The various hydrocarbon feeds exemplified in the above tables should of course be considered as illustrative and not limiting of the invention. Any other suitable hydrocarbon feed can be used. For example, cracking products of petroleum waxes including cracking products of Fischer-Tropsch waxes. These waxes are derived from the distillate fraction of lubricating oils and melt at relatively low temperatures up to about 72°C, such as from about 50°C to about 70°C, and contain from about 18 to about 36 carbon atoms. These waxes preferably contain 50% to 90% n-alkanes and 10% to 50% monomethyl branched alkanes and low levels of various cyclic alkanes. These cleavage product feeds are especially useful in alternative embodiments of the present invention (as will be described hereinafter and in "Chemical Economics Handbook" published by SRI, Menlo Park, California). See, eg, "Waxes", S595.5003 L, published 1995. Paraffin waxes are also described in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Edition (1984), Volume 24. See "Waxes" on page 473. Any equivalent alternative hydrocarbon feed or more preferably a short chain equivalent in the C10-C20 range with suitable monomethyl branching anywhere along the chain, such as those from Fisher-Tropsch synthesis are also suitable.

The hydrocarbon feed here can contain varying amounts of N.O.S. impurities. Certain preferred hydrocarbon feeds (especially if derived from sulfur and/or nitrogen containing fractions) are desulfurized and/or liberated nitrogenous species using conventional desulfurization or "de-NOS" techniques.

The hydrocarbon feed here can be separated prior to use in the process so that a large amount of hydrocarbons with a specific chain length and/or degree of branching can be most efficiently used to produce modified alkylbenzenes and/or modified primary OXO alcohol. For example, although not specifically indicated in the figure, it should be necessary to employ two paraffinic cuts from kerosene for two essentially parallel processes, each described here, one including an alkylation stage to form modified Alkylbenzene, a modified primary OXO alcohol that includes an OXO stage formation. In such a dual process, it may often be preferable to use a cut with a lower total carbon number to produce alkylbenzenes (such as a cut rich in C11-C13 hydrocarbons), while a heavier cut, such as a cut rich in C14-C17 hydrocarbons Parts of can be used to prepare modified OXO alcohols. Alternative methods include the use of multiple hydrocarbon streams or cuts for parallel production of modified and non-modified (conventional) alkylbenzenes and/or OXO alcohols. Adsorption separation step

In general, separation techniques in the process steps of the invention rely on adsorption on porous media and/or employing clathrating agents. A landmark patent on adsorptive separations is US 2,985,589, which describes the various equipment, adsorbent beds, and process conditions of temperature and pressure generally applicable here. The patent does not describe the various key improvements, particularly pore size and linkage of steps for specific separations, which are part of the present invention.

In general, the adsorption separation steps can be carried out in the gas or liquid phase, with or without the use of commercial processing equipment such as those described in the Background of the Invention.

In general, porous media used as adsorbents may or may not be dried. Preferred embodiments include those wherein the sorbent is dried and contains less than about 2% moisture.

Any adsorptive separation step according to the invention may or may not use a desorbent or displacer. In general, any desorption device such as a pressure swing or other device can be used. However, the use of such desorbents is preferred, in other words, solvent displacement is a preferred method of desorbing streams from the porous media used here. Suitable desorbents or displacers include various low molecular weight n-paraffins such as heptane, octane, etc., or polar desorbents such as ammonia. It should be understood that such well-known and entirely conventional desorbents, whether present or not, cannot be expressly included in any stream or its various compositions in the description of the process herein, and may be employed as desired. The desorbent cycle steps shown in Figures 1-18 are cycled.

In the process of the invention, stage (a) may use UOP's ^MOLEX® process step, with the difference that the process of the invention must have at least one zeolite with a pore size larger than that typically used in the production of linear alkylbenzenes, which is typically 5 Angstroms. Porous materials are separated by adsorption. ^MOLEX® is discussed in the aforementioned Surfactant Science Series, Volume 56 (including, for example, pages 5-10). Various gas phase methods such as Union Carbide's IsoSiv method (see same reference) are also useful but less preferred.

The equipment and operating conditions for the ^MOLEX® process are well known in whatever form used herein; see for example the above references at page 9 for a detailed description of the various processes and their various streams, including raffinate and adsorbent . Porous media (large pore type)

The porous media required here in stage (a) is of the large pore type. "Large pore size" specifically means that the pore size of the porous medium is large enough to intercept monomethyl-branched linear olefins or paraffins and dimethyl-branched or trimethyl-branched linear olefins or paraffins (except geminal dimethyl hydrocarbons) ), but small enough to at least partially exclude gem-dimethyl, ethyl, and higher branched hydrocarbons, as well as cyclic (eg, 5-, 6-membered rings) and aromatic hydrocarbons. This pore size, which is large enough to trap a suitable amount of methyl branched hydrocarbons, is not used in conventional linear alkylbenzene production, and is hardly used in any industrial process compared to the more common 4-5 angstrom pore size zeolites . Large pore size porous media are those used in Figures 1-7 in the adsorption separation unit labeled "SOR 5/7".

Thus, here the minimum pore size of the predominantly porous media in stage (a) is greater than that required for the selective adsorption of linear acyclic hydrocarbons, i.e. exceeding those used in conventional linear alkylbenzene production, which The size is no greater than about 20 angstroms, more preferably no greater than about 10 angstroms, most preferably an average of more than about 5 angstroms to about 7 angstroms. When specifying the minimum pore size for use in so-called "large pore" porous media herein, it should be understood that such materials generally have elliptical pore sizes, such as SAPO-11 with a pore size of 4.4 x 6.7 angstroms (average 5.55 angstroms) . See S. Miller, Micropoms Materials, Vol. 2, pp. 439-449 (1994). When comparing this material with "small pore size" zeolites such as 4-5 angstrom uniform pore size zeolites, when making size comparisons, the convention here is to treat the average size of the ellipsoids or the size of the larger ellipsoids as one Not a smaller oval size under any circumstances. The SAPO-11 material is thus defined herein as a zeolite with a uniform pore size greater than 5 Angstroms.

The predominant porous medium with relatively large pore size in stage (a) here can be either zeolite (aluminum silicate) or non-zeolite.

Suitable non-zeolites include the various silicoaluminophosphates, especially SAPO-11, although others may be used if the average pore size is greater than about 5 angstroms or if ellipsoidal pore sizes are present with at least one elliptical dimension exceeding 5 angstroms. Silicoaluminophosphate.

Another technique suitable for adsorptive separations here is sorption with pyrolyzed poly(1,1-dichloroethylene), i.e. pyrolyzed SARAN (produced as such according to Netherlands Application NL 7111508, published October 25, 1971). technology. Preferred materials have a sieve diameter of 4-7 Angstroms. When using this material as the primary adsorbent, pore sizes in excess of about 5 Angstroms will be used. Use of organometallic-grafted mordenite and other grafted zeolites as porous media in stage (a)

The invention also encompasses particularly useful embodiments in which the adsorptive separation of stage (a) comprises at least one separation step employing organometallic-grafted mordenites. Porous media particularly suitable as "large pore size" herein are grafted mordenites such as tin grafted mordenites. Similarly and more generally the present invention encompasses a process comprising the use of grafted mordenite for the production of detersive surfactants and any corresponding surfactants and by using these specific porous Living products prepared by medium. See EP 559,510 A9/8/93 which is hereby incorporated by reference in its entirety. Those skilled in the art will be able to select the grafted mordenites of these EP 559,510 (as is clear from its examples) for use in optimum form for converting linear and monomethyl branched hydrocarbons from gem dimethyl and polymethyl separated from hydrocarbons.

Other grafted zeolites useful as porous media herein include those of US 5,326,928, also incorporated herein by reference in its entirety. In this embodiment of the invention, it is especially preferred to combine the following two steps into a single process: in stage (a) using the grafted mordenite described above, and in step (c) (herein otherwise partly defined as At least partially dealuminated H-mordenite is used in the alkylation step).

On this basis, the terminology of US 5,326,928 is used to describe a process module (module) containing a grafted component in combination with the preferred alkylation steps defined therein, and the invention also includes methods for the preparation of modified alkylbenzenes and/or or a modified alkylbenzenesulfonate process comprising: (a) at least one separation of aliphatic paraffins having varying degrees of branching in a hydrocarbon feed containing molecules of 9 to 14 carbon atoms into at least one A first effluent comprising less branched (linear and monomethyl, optionally some dimethyl branched) paraffins and at least one comprising more branched (trimethyl and higher-branched) paraffins paraffins and optionally cyclic and/or aromatic impurities) stage; said separation comprises separating the hydrocarbon feed with at least one comprising at least one grafted organometallic compound (the amount and (b) at least one stage (a) stage of less branched effluent alkylation, preferably carried out in an alkylation with an endoisomer selectivity of 0-40, more preferably with at least partially dealuminated, at least partially acidic H-mordenite as a catalyst; and (c) at least one stage in which the product of stage (b) is sulfonated using any conventional sulfonating agent. The resulting modified alkylbenzene sulfonic acids can be neutralized and incorporated into cleaning products (as described elsewhere herein).

In stage (a) of the process according to the invention, the zeolite or other porous medium is preferably used in such a form that it does not promote chemical reactions of the starting materials, such as cracking, polymerization, etc. Therefore, acidic zeolites are preferably avoided in stage (a). See the alkylation catalysts hereinafter for comparison, of which the at least partially acidic form is preferred. Porous media (smaller pore size type)

Zeolites of smaller pore size can optionally be used in stage (a) here, such as those used in the adsorption separation units labeled "SOR 4/5" in Figures 1, 2, 5, 6, which selectively adsorb linear hydrocarbons rather than Does not adsorb methyl-branched hydrocarbons. Such porous materials are well known and include, for example, calcium zeolites having a pore size of 4-5 Angstroms. Such materials are further described in US 2,985,589 and are those currently used commercially for the production of shaped alkylbenzenes. Porous media (such as OLEX_ or similar method)

When preparing the modified primary OXO alcohols herein, it may be preferred to carry out an olefin/paraffin separation step in stage (C) to concentrate the monoenes. See "SOR O/P" in the figure and stage (C) in the claims. Suitable porous media for this stage include copper treated or silver treated zeolite X or zeolite Y. See eg US 5,300,715 or US 4,133,842 (cited here). See also US 4,036,744 and US 4,048,111. Alternatively, UOP Corp. (technical registrant) has an entire approach called OLEX_ available that is available. Caging

As is known in the prior art, urea clathration can be used here in stage (a) to separate n-paraffins from branched paraffins. See, eg, Surfactant Science Series, Marcel Dekker, N.Y., 1996, Vol. 56, pp. 9-10 and various references therein. See also "Manufacture of Detergents Including Zeolite Builders and Other New Materials", Ed. Sittig., Noyes Data Corp., 1979, pp. 25-30, especially US 3,506,569, which is hereby incorporated by reference in its entirety (It uses solid urea but no chlorinated hydrocarbon solvent). The more general but less preferred method according to US 3,162,627 can be used. dehydrogenation

In general, the dehydrogenation of olefins or olefin/paraffin mixtures in the process of the present invention can be accomplished using any of the well-known dehydrogenation catalyst systems, including those described in the Surfactant Science Series references cited in the background information and Those systems and other dehydrogenation catalyst systems described in "Production of Detergents Including Zeolite Builders and Other New Materials", Ed. Sittig., Noyes Data Corp., New Jersey, 1979, are available, for example, from UOP Corp. those industrial products purchased in Dehydrogenation can be performed in the presence of hydrogen, usually in the presence of a noble metal catalyst (such as DeH-5, DeH-7, DeH-9 commercially available from UOP), although alternative non-hydrogen, noble metal-free Dehydrogenation systems such as zeolite/air systems (no precious metals present).

More specifically, dehydrogenation catalysts useful herein include catalysts supported on Sn-containing alumina and having Pt: 0.16%, Ir: 0.24%, Sn: 0.50%, and Li: 0.54% (as incorporated by reference described in US 5,012,027 herein). When this catalyst was contacted with a mixture of C9-C14 paraffins (believed to be linear) at 500°C and 0.68 atm, the olefin product was obtained with a selectivity of 90.88% and a conversion of 11.02% (38 hours on stream), which we believe to be quite Suitable here for at least partial dehydrogenation of paraffin-rich branched streams. See also US 4,786,625, EP 320,549 A1 6/21/89; Vora et al., Chem. Age India (1986), 37(6), pp. 415-18.

As noted above, the dehydrogenation may be complete or partial, more typically partial dehydrogenation. When partial dehydrogenation is carried out, this step results in a mixture of olefins (eg about 10%, this data is for illustration only and should therefore not be considered limiting) with equilibrated unreacted paraffins. This mixture is a suitable feed to the alkylation step of the process of the present invention.

Other useful dehydrogenation systems that are readily suitable in the present invention include those of US 4,762,960 (incorporated herein by reference), which discloses a compound having a modifying metal, alkali metal , alkaline earth metals or their mixtures, Pt-group metal-containing dehydrogenation catalysts and specific refractory oxide supports.

Various alternative dehydrogenation catalysts and conditions useful herein include those in US 4,886,926 and US 5,536,695. Alkylation

An important embodiment of the present invention also includes alkylation by delinearization of the separated enriched lightly branched paraffins and at least partial dehydrogenation of said delinearized olefins or olefin/paraffin mixtures. Alkylation is carried out with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof. Internal isomer selectivity and choice of alkylation step

A preferred embodiment of the process of the invention requires an alkylation step with an internal isomer selectivity of 0-40, preferably 0-20, more preferably 0-10. For any given alkylation process step, internal isomer selectivity, or "IIS," as defined herein, is determined in a 1-dodecene alkylation test using benzene in a molar ratio of 10:1 . The alkylation is carried out in the presence of an alkylation catalyst to convert at least 90% of the dodecene and produce at least 60% of the monophenyldodecane. The internal isomer selectivity was then determined as follows:

Wherein quantity is the quantity (weight) of product; The quantity of final phenyldodecane is the sum of 2-phenyldodecane and 3-phenyldodecane quantity, and the total amount of phenyldodecane is 2- The sum of phenyldodecane plus 3-phenyldodecane plus 4-phenyldodecane plus 5-phenyldodecane plus 6-phenyldodecane, where said amount is determined by any known Determined by analytical techniques such as gas chromatography for alkylbenzene sulfonates. See Analytical Chemistry, November, 1983, 55(13), pp. 2120-2126, Eganhouse et al., "Determination of Long-chain alkylbenzenes". When calculating IIS from the above formula, the quantities are divided, the result is subtracted from 1 and multiplied by 100. It will of course be understood that the specific alkene used to identify or test the suitability of any given alkylation procedure is a control against which the alkylation procedure herein can be compared to various known methods for preparing linear alkyl groups. Alkylation steps of benzene are compared and enable the practitioner to determine whether a given known alkylation step can be used in the series of process steps making up the present invention. In carrying out the process of the present invention, the hydrocarbon feed for the alkylation step actually employed is of course determined according to the preceding process steps. It should also be noted that all current industrial processes for producing LAS differ from the preferred embodiment of the present invention solely on the basis of the IIS employed in the alkylation step. For example, the IIS of various LAS methods based on aluminum chloride, HF, etc. are all outside the scope specified by the method of the present invention. On the contrary, several alkylation steps which are described in this literature but are not currently used in the industrial production of alkylbenzenesulfonates have suitable IIS and can be used in the present invention.

To better assist the practitioner in determining IIS and deciding whether a given alkylation step is suitable for the purposes of the present invention, the following is a more specific example of determining IIS.

Alkylation of benzene by 1-dodecene was carried out at a molar ratio of benzene to 1-dodecene of 10:1 as described above and the alkylation was in the presence of an alkylation catalyst This is done so that at least 90% of the dodecene is converted and at least 60% of the monophenyldodecane is produced. In general, the alkylation test must be carried out at a reaction time of less than 200 hours and a reaction temperature of about -15°C to about 500°C, preferably about 20-500°C. The range of pressure and catalyst concentration relative to 1-dodecene is wide. No solvents other than benzene were used in the alkylation experiments. Various process conditions for the catalyst or IIS for the alkylation step can be determined based on this literature. The practitioner can generally adopt suitable conditions based on a large variety of detailed data for alkylation. For example, if _AlCl3 alkylation could be used here, various suitable process conditions were determined to be 1-dodecene with 5% (mole, relative to 1-dodecene) at 20-40°C ) AlCl ₃ was reacted in a batch reactor for 0.5-1.0 hours. This experiment shows that the _AlCl3 alkylation step is not suitable for use in the process of the present invention. IIS should be about 48. In another example, a suitable alkylation experiment using HF as a catalyst should have an IIS of about 60. Therefore, neither _AlCl3 alkylation nor HF alkylation is within the scope of the present invention. For medium pore zeolites such as dealuminated mordenite, suitable process conditions for the determination of IIS are, for example, obtained by reacting 1-dodecene and benzene in a molar ratio of 10:1 at a WHSV of 30 h ^-1 at a reaction temperature of approximately Flowing through the mordenite catalyst at 200°C and a pressure of about 200 psig will result in an IIS of about 0 for the mordenite catalyst. The temperatures and pressures used for the exemplary mordenite alkylation tests (see also the various detailed examples of the method of the invention hereinafter) can be used more generally for testing various zeolites and other shape selective alkylation catalysts. Using a catalyst such as H-ZSM-4 should give an IIS of about 18. It is clear that both dealuminated mordenite and H-ZSM-4 catalyzed alkylation yield acceptable IIS for the present invention, preferably mordenite.

Without wishing to be bound by theory, it is believed that the low-IIS alkylation step performed with the H-mordenite herein can alkylate benzene with branched rich hydrocarbons, but it is less effective for scrambling attachment to hydrocarbon chains. The position of the methyl branch on is also quite useful. Alkylation catalyst

The IIS required in the alkylation process step can be obtained by strictly controlling the selection of the alkylation catalyst. It was readily determined that large amounts of alkylation catalyst were not suitable. Various unsuitable alkylation catalysts include ^DETAL® process catalysts, aluminum chloride, HF, HF on zeolites, fluorinated zeolites, non-acidic calcium mordenites, and many others. In fact, we have thus far found that none of the alkylation catalysts currently used commercially for the alkylation of linear alkylbenzene sulfonates in detergents is suitable.

Instead, suitable alkylation catalysts here are selected from shape selective moderately acidic alkylation catalysts, preferably zeolites. The zeolite in this catalyst for the alkylation step (step (b)) is preferably selected from the group consisting of mordenite, ZSM-4, ZSM-12, ZSM-20, zeolite, gmelinite in at least partially acidic form and beta-zeolite. More preferably the zeolite in step (b) (alkylation step) is substantially in the acid form and is contained in catalyst particles comprising a conventional binder, wherein the catalyst particles comprise at least about 1%, more preferably at least 5 %, usually more preferably from 50% to about 90% of said zeolite.

More generally, suitable alkylation catalysts are usually at least partially crystalline, and more preferably crystalline, substantially free of binders or other materials used to form catalyst particles, aggregates or compositions. Furthermore, the catalyst is usually at least partially acidic. For example, the fully exchanged Ca-form of mordenite is not suitable, while the H-form of mordenite is suitable. This catalyst can be used in the alkylation step designated as step (b) in the claims hereafter: it corresponds to step 7 in FIG. 1 .

The pore size characteristics of the zeolites useful in the alkylation process of the present invention can be substantially circular, as in cancryptite with a uniform pore size of about 6.2 angstroms, or preferably can be somewhat elliptical, as in The situation in mordenite. It is to be understood that, in any event, the major pore sizes of the various zeolites used as catalysts in the alkylation step of the process of the present invention are between the larger pore size zeolites (such as X and Y zeolites) and the smaller pore size zeolites (such as ZSM-5 and ZSM-11), preferably between about 6 Angstroms and about 7 Angstroms. We have actually tried ZSM-5, but found it unable to operate in the present invention. The pore size dimensions and crystal structures of certain zeolites are specified in the Zeolite Structure Type Atlas published by the Structure Commission of the International Zeolite Association (1978 and many reprints) and distributed by the Polycrystal Book Service, Pittsburgh, Pa. (W.M.Meier and D.H. Olson).

Zeolites useful in the alkylation step of the process of the invention generally have at least 10% of the cationic sites occupied by ions other than alkali metals or alkaline earth metals. Common, but non-limiting, replacement ions include ammonium, hydrogen, rare earth metals, zinc, copper, and aluminum. Among this series, ammonium, hydrogen, rare earth metals or various combinations thereof are particularly preferred. In a preferred embodiment, the zeolite is converted to a predominantly hydrogen form (the form obtained by calcination), typically by replacing the pre-existing alkali metal or other ions with a hydrogen ion precursor, such as ammonium ions. This exchange is conveniently carried out by contacting the zeolite with a solution of an ammonium salt, such as ammonium chloride, using well known ion exchange techniques. In certain preferred embodiments, the degree of substitution is such that a zeolite material is obtained in which at least 50% of the cationic sites are occupied by hydrogen ions.

Zeolites can be subjected to a variety of chemical treatments, including alumina extraction (de-alumination) and association with one or more metal components, particularly metals of Groups IIB, III, IV, VI, VII, and VIII. It will also be appreciated that in some cases the zeolite may be thermally treated as desired, including steaming or calcining in air, hydrogen or an inert gas such as nitrogen or helium.

Suitable modification treatments require steaming the zeolite by contacting it with an atmosphere at a temperature of from about 250°C to 1000°C, containing from about 5% to about 100% steam. Steaming can last from about 0.25 to about 100 hours and can be performed at pressures ranging from subatmospheric to several hundred atmospheres.

In carrying out the alkylation step required by the present invention, the above-mentioned intermediate pore size crystalline zeolites may be incorporated into another material such as a binder or a matrix resistant to the temperature and conditions used in the process of the present invention . Such matrix materials include synthetic or natural substances as well as various inorganic materials such as clays, silica and/or metal oxides. Matrix materials can be in the form of various gels, including mixtures of silica and metal oxides. The latter can be in natural form or in the form of a gel, or gel-like precipitate. Natural clays that can be combined with zeolites include the montmorillonite and kaolin series, which includes various subbentonites and kaolins, such as the well-known Dixie, McNamee-Georgia and Florida clays, or others where the main inorganic components are halloysite, kaolin Those of ridgeite, dickite, nacrite or silica-rich kaolinite. This clay can be used in the raw state, in the form originally mined or initially calcined, acid-treated or chemically modified.

In addition to the above materials, the intermediate pore size zeolites used herein can be combined with porous matrix materials such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica- Thorium oxide, silica-beryllia and silica-titania and ternary combinations such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and Silica-magnesia-zirconia and other compositions. The matrix may be in co-gelled form. The relative proportions of the finely divided zeolite to the inorganic oxide gel matrix can vary widely, and the zeolite content can range from about 1% to about 99% by weight of the composite, more typically from about 5% to about 80% by weight. ).

A group of zeolites, including some useful in the alkylation step herein, have a silica:alumina ratio of at least 10:1, preferably at least 20:1. The silica:alumina ratio referred to in this specification is the structure or framework ratio, ie the ratio of SiO4 to AlO4 tetrahedrons. This ratio can vary depending on the silica:alumina ratio determined by various physical and chemical methods. For example, the overall chemical analysis may involve cationic attachment to acidic sites on the zeolite, thereby resulting in a low silica:alumina ratio. Similarly, if the ratio is determined by thermogravimetric analysis (TGA) of deamination, low ammonia titers will be obtained if the cationic aluminum prevents ammonium ion exchange to acid sites. These geometrical differences lead to rather troublesome consequences when certain treatments such as dealumination as described below (resulting in aluminum ions outside the zeolite structure) are used. Care should therefore be taken to ensure that the silica:alumina ratio in the framework is correctly determined.

Beta-zeolites suitable for use herein (but less preferred than H-mordenite) are disclosed in US Patent No. 3,308,069, which describes such zeolites and methods for their preparation in detail. The acidic form of this zeolite is also commercially available as Zeocat PB/H from Zeochem.

When zeolites are prepared in the presence of organic cations, these zeolites are catalytically inactive, probably because the free space within the crystals is occupied by organic cations from the forming solution. It is activated by heating at 540°C for 1 hour in an inert atmosphere, followed by base exchange with the ammonium salt, followed by calcination at 540°C in air. The presence of organic cations in the forming solution may not be absolutely necessary for the formation of zeolites; but appears to favor the formation of this particular type of zeolites. Some natural zeolites can sometimes be converted to the desired type of zeolites by various activation methods and other various treatments such as base exchange, steam heating, alumina extraction and calcination. Preferred zeolites have a crystalline framework density (in the form of dry hydrogen) of not substantially less than about 1.6 g/ ^cm3 . Dry densities for known structures can be calculated from the sum of silicon and aluminum atoms per 1000 ^Angstroms (as included in "Proceedings of the Conference on Molecular Sieves, London, 1967), published by the Society of Chemical Industry (London, 1968) April 2019, p. 19 in the article by WMMeier on the structure of zeolites). Refer to that paper for a discussion of crystalline framework density. See also US Patent No. 4,016,218 for a discussion of crystalline framework density and values for some typical zeolites. When the zeolite is synthesized in the alkali metal form, it is conveniently converted to the hydrogen form (generally by ammonium ion exchange to an intermediate in the ammonium salt form, followed by calcination of the ammonium salt form to the hydrogen form). The zeolite may also be partially in the alkali metal form, although we have found that the hydrogen form of the zeolite can successfully catalyze the reaction.

EP 466,558 describes an alkylation catalyst of the acidic mordenite type which can also be used here, with an overall Si/Al atomic ratio of 15-85 (15-60) and a Na weight content of less than 1000 ppm (preferably less 250ppm), with low or no content of Al species outside the network, the elementary mesh volume is less than 2,760 nm ³ .

US 5,057,472, which can be used to prepare the alkylation catalysts herein, relates to the simultaneous dealumination and ion exchange of an acid-stable sodium ion-containing zeolite, preferably mordenite, by contacting 0.5-3 (preferably 1-2.5) M with sufficient NH ₄ NO ₃ in HNO ₃ solution is contacted so that Na ions can fully exchange NH ₄ and H ions to achieve). The resulting zeolite has a _SiO2 : _Al2O3 ratio of 15-26 (preferably 17-23):1 and is preferably calcined to at least partially convert the _NH4 /H form to _the H form. Although not specifically required in the present invention, optionally the catalyst may contain a Group VIII metal (and optionally an inorganic oxide) and the calcined zeolite of the above patent.

Another acidic mordenite catalyst useful in the alkylation step herein is disclosed in US 4,861,935 which relates to the hydrogen form of mordenite bound to alumina, the composition having a surface area of at least 580 ^m2 /g. Other acidic mordenite catalysts useful in the alkylation step herein include those described in US 5,243,116 and US 5,198,595. Yet another alkylation catalyst useful herein is described in US 5,175,135, which is a silica/alumina molar ratio of at least 50:1 and a symmetry index of at least 1.0 (determined by X-ray diffraction analysis) and an acidic mordenite having a porosity such that the total pore volume is from about 0.18 cc/g to about 0.45 cc/g and the ratio of mixed mesopore and macropore volume to total pore volume is from about 0.25 to about 0.75.

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

Most generally, any alkylation catalyst can be used here, provided that the alkylation step meets the various requirements for internal isomer selectivity described above. Distillation of modified alkylbenzenes or modified primary OXO alcohols

Depending on the raw materials used and the specific sequence of steps, the process of the present invention may optionally include distillation of the modified alkylbenzene or modified primary OXO alcohol, for example to remove unreacted raw materials, paraffins, excess benzene, and the like. Any conventional distillation equipment can be used. The general procedure is similar to that used for distillation of commercial linear alkylbenzene (LAB) or OXO alcohols. Suitable distillation procedures are described in the above referenced Surfactant Science Series eg "Review of Alkylbenzene Sulfonate Production". Sulfonation/sulfation and post-treatment (Workup)

In general, the sulfonation of modified alkylbenzenes or the sulfation of modified primary OXO alcohols (or their alkoxides) in the process of the present invention can be accomplished using any well-known sulfonation system, including the above-referenced "Manufacture of Detergents Including Zeolite Builders and Other New Materials" and "Review of Alkylbenzene Sulfonate Production" by Surfactant Science Series, referenced above. Common sulfonation systems include sulfuric acid, chlorosulfonic acid, oleum, sulfur trioxide, etc. Sulfur trioxide/air is especially preferred. Details of sulfonation using suitable air/sulfur trioxide mixtures are described in US 3,427,342 to Chemithon. The sulfonation process is also extensively described in "Sulphonation Technology in the Detergent Industry", W.H. de Groot, Kluwer Academic Publishers, Boston, 1991.

Any convenient post-processing step may be used in the methods of the invention. The usual practice is to neutralize with any suitable base after sulfonation. The neutralization step may thus be carried out using a base selected from the group consisting of sodium, potassium, ammonium, magnesium and substituted ammonium bases and various mixtures thereof. Potassium aids in solubility, magnesium enhances water softening performance, and substituted ammonium aids in the formulation of various surfactants tailored to the invention. The present invention includes any modified alkylbenzene sulfonate surfactants prepared by the process of the present invention, or sulfated modified primary OXO alcohols or derivatives of alkoxylated, sulfated modified primary OXO alcohols and their Use in lifestyle product compositions.

Alternatively, the acidic form of the surfactants of the invention can be added directly to acidic cleaning products, or can be mixed with the individual cleaning ingredients and then neutralized. post-alkylation step

As noted above, the inventive process herein includes embodiments having various steps performed after the alkylation step (c). Preferably these steps comprise (d) sulfonating the product of step (c); and one or more steps selected from: (e) neutralizing the product of step (d); and (f) converting step (d) or The product of (e) is mixed with one or more cleaning product additive materials; thereby producing a cleaning product. Blended Embodiment

In a preferred embodiment, the modified alkylbenzene which is the product of said step (c) is blended with linear alkylbenzene prepared by conventional methods prior to said sulfonation step. In another such embodiment, in any step after said sulfonation step, the modified alkylbenzene sulfonate that is the product of said step (d) is mixed with linear alkylbenzene prepared by conventional methods Blend. In these blended embodiments, the preferred process has a ratio of modified alkylbenzene to linear alkylbenzene of from about 10:90 to about 50:50.

A corresponding blending scheme applies of course to the modified primary OXO alcohol process here. In addition, various types of surfactants herein or their precursors may be blended. For example, the practitioner is free to blend modified alkylbenzenes with the modified primary OXO alcohols prepared here, alkoxylated mixtures with ethylene oxide, propylene oxide, etc., then sulfate/sulfonate to final mixture. Additionally, in general, modified OXO alcohols can be isolated by distillation, and various other OXO alcohol types, including linear OXO alcohols, are known in the art, and the invention also encompasses blending modified or branched alcohols available herein in any proportion. OXO alcohols and any known OXO alcohols (such as branching from about 1:100 to about 100:1 (by weight): linear OXO alcohols), and converting such OXO alcohol blends into surfactants suitable for use in detergents agent method. Other method implementations

The present invention also includes a process for treating waste streams from the production of linear alkylbenzene sulfonate surfactants for use in cleaning products, said process comprising (i) at least partially separating isoparaffins into A n-paraffin-containing stream and a waste stream rich in isoparaffins (particularly methyl branched paraffins) comprising at least about 10% isoparaffins and having a molecular weight of at least about 128 and not more than about 282, wherein all Said separation comprises at least one step selected from the group consisting of clathration by urea and separation by sorption, wherein said steps are necessary in a process for the production of linear alkylbenzenes; (ii) by at least one a step selected from urea clathration and sorption separation to at least partially re-enrich the isoparaffin content of said waste stream; wherein said step is an additional step and follows step (i); and (iii) at least in part A step of dehydrogenating the isoparaffin-rich stream of step (ii).

More generally, we expect the hydrocarbons prepared here to be useful not only in modified alkylbenzene sulfonate surfactants as non-limiting illustrative examples, but also in modified alkylbenzene sulfonate surfactants other than alkylbenzene sulfonates. Active surfactants (such as alkyl sulfates). Accordingly, the present invention also includes a method for treating a branched paraffin waste stream comprising (i) at least partially separating isoparaffins into a stream rich in n-paraffins and a stream comprising at least about 10% isoparaffins A waste stream rich in isoparaffins, wherein said separation comprises at least one step selected from the group consisting of clathration by urea and separation by sorption; The step of separating at least partly re-enriches the isoparaffin content of said waste stream; wherein said step is an additional step and follows step (i); and (iii) at least partly results in said step (ii) A step for the dehydrogenation of a stream rich in isoparaffins.

In such an embodiment, the isoparaffin-rich stream may have a total carbon content of from about C10 to about C20, and the non-linear portion of the enriched stream includes an average of about 1 to about 2 methyl groups per molecule. Side chains (other than terminal methyl side chains), the non-linear portion of the enriched stream preferably includes less than about 30%, more preferably less than about 10%, and still more preferably less than about 1% Carbon atoms of the molecules and less than 50%, preferably less than about 10%, more preferably less than about 1% of the molecules have gem dimethyl substitution. Embodiment combined with carbonylation (OXO reaction)

As mentioned in the overview, the present invention also includes embodiments that involve the selective conversion of hydrocarbons by certain adsorptive separations into novel and useful poly(alkoxylated)sulfates and poly(alkoxylated)sulfates for the production of other soluble sulfates. (alkoxylate) modified primary OXO alcohols. These are given as examples only. Of course, modifications of other surfactant types known in the art derived from OXO are also included in the present invention. According to such an embodiment broadly in the review, the preferred process here has a stage (A) apparatus comprising one, two or more of said apparatuses and at least two of said beds, at least The amount of porous media differs from one said bed to the other by the increased ability to hold methyl-branched cycloaliphatic hydrocarbons. However, it is preferred that stage (D) comprises a one-step OXO stage, wherein the OXO catalyst is a transition metal (other than iron) coordinated to the phosphine.

In more detail, in this preferred process at least one of said beds comprises porous media normally used for the production of paraalkylbenzene; at least one of said beds is connected to said process and is adapted to at least partially increase The proportion of methyl-branched open-chain aliphatic hydrocarbons in the stream of said stage (B) of said process is adapted to at least partially reduce the linear open-chain in the stream entering said stage (B) of said process The proportion of aliphatic hydrocarbons which are at least partly removed in said stage (A) in the form of a linear-rich stream.

For convenience, in one such process embodiment, in said stage (A), said simulated moving bed adsorptive separation unit comprises - a said apparatus, provided that said apparatus is capable of simulating in at least one bed at least two of said devices, or the movement of said porous medium in at least two of said devices.

Also included herein is a method wherein there are two of said devices in at least one bed, each comprising a different element of said porous media, said at least one bed being each controlled by one of said devices, said devices each having A minimum of 8 outlets are used to simulate the movement of said porous media in said at least one bed. See Figure 9, where unit SOR4/5 includes one class of porous media (defined in more detail elsewhere herein), and unit SOR 5/7 includes another type. "Apparatus" refers to particular rotary valve apparatuses that may be selected from among others (details are described in the various patents indicated in the "Background" section). See also Figure 8, which, although more specifically depicting the process with an alkylation step, also shows in more detail the rational arrangement of the adsorptive separation unit, rotary valves and ancillary equipment. It should be understood here that the adsorption media and equipment are each known; what matters is the choice of equipment and how they are connected, which is the key to the present purpose of obtaining superior OXO alcohols and derivatized surfactants.

The present invention therefore also includes a process for the production of OXO alcohols, wherein said linear-enriched stream is present in said stage (A), said stage (A) comprising: (A-i) passing through one of said simulated beds Adsorptive separation apparatus for adsorptively separating said hydrocarbon feed into a linear-rich stream and an intermediate branch-rich stream and withdrawing said linear-rich stream; then (A-ii) by another simulated moving bed adsorption separation means for adsorptively separating said intermediate branch-enriched stream into said branch-enriched stream containing an increased proportion of branched open-chain aliphatic hydrocarbons relative to said intermediate branch-enriched stream, said discharge stream comprising at least Increased proportion of cyclic and/or aromatic hydrocarbons (relative to the branched rich stream).

Preferably in such an embodiment, all of said beds comprise porous media not conventionally used for the production of linear alkylbenzenes (such as SAPO-11 included in unit SOR 5/7 or other equivalent for the production of linear alkylbenzenes molecular sieves), the porous medium added to the process has a pore size suitable for at least partially increasing the proportion of methyl branches and linear open-chain aliphatic hydrocarbons in the stream passing through said step (B) of the process, Said hydrocarbons other than said linear and methyl-branched hydrocarbons are at least partly removed in stage (A) in the form of an effluent stream.

In the production embodiment of the OXO alcohol of the present invention, the hydrocarbon feed suitably comprises at least about 10% methyl branched paraffins (molecular weight of at least 128 and no greater than 282). See tables elsewhere herein for additional descriptions of suitable feeds.

In the OXO process herein, the crude feed is preferably distilled prior to use. A non-limiting example is illustrated by a distillation unit beginning with the process shown in Figures 9-18. In this embodiment, the hydrocarbon feed (as it passes from the distillation unit to the rest of the process) comprises a narrow cut (in the C10-C17 range) of no more than three carbon atoms, preferably no more than two carbon atoms. Inside). This cut may be a single carbon cut, a two carbon cut, a three carbon cut or a cut comprising an imprecise range of carbon numbers such as a one-and-one-half carbon cut, suitable for the cut Examples are the C11-C13 cut, the C14-C15 cut and the C15-C17 cut, although it is not intended to exclude other cuts such as the C16.5 cut. These cuts, designated as non-integer numbers, can be produced by methods such as mixing shorter and longer one-carbon number fractions. Thus the C16.5 cut can be prepared by mixing C16 and C17 or by mixing C14 and C17, etc. Preferred cuts have a narrower "stretch" of carbon numbers in the mixture. Alternatively, the distillation may be used directly on the olefinically rich sidestream to produce the desired cut just prior to the OXO reaction of the olefinically rich sidestream.

For practical purposes, it should be understood that when distilling hydrocarbons herein, the desired methyl branched hydrocarbons generally have lower boiling points than linear hydrocarbons having the same carbon number. Thus, a preferred cut boiling between the linear C15 and linear C16 paraffins will be enriched in the methyl branched isomers having a total carbon number of 16 which are desired in the process.

Unusually, if not exclusively, for the production of OXO alcohols, the hydrocarbon feed is an adsorptively separated paraffin derived from either a linear alkylbenzene production process or a conventional linear detergent alcohol process. That is, the present invention opens up all new possibilities of combining linear alkylbenzene production and/or conventional linear detergent alcohol processes with OXO alcohol production processes to be implemented hereafter. It achieves a better utilization of the feed. In addition, novel alkylbenzenes and OXO alcohols can be obtained when employing the invention described herein. They can be performed alone, or they can be interchanged with conventional linear alkylbenzenes and/or OXO alcohols by rationalizing the apparatus using the procedures described here.

Once the modified primary OXO alcohol is made, it can of course be converted to another useful derivative either in the same plant or in another separate plant. For example, the process may have additional stages selected in order from: (E) sulfation and neutralization of the product of said stage (D); (F) alkoxylation of said product of stage (D); and (G) alkoxylation , sulphating and neutralizing the product of said stage (D).

Furthermore, once surfactant derivatives of the type described above are prepared, they can be readily incorporated into cleaning compositions in their entirety. For this purpose, co-locating the above-mentioned devices or devices placed separately, the method may have a further step (H) - mixing the product of the previous stage with one or more cleaning product additive materials; thereby forming a cleaning product.

Although, as can be seen from the Background Art section, various OXO alcohols are already known (see eg the Shell and/or Sasol process), no specific adsorptive separation specified here prior to the OXO stage has been suggested before. Also, there is no suggestion here to use the unused portion of the stream provided by the production of linear alkylbenzenes (at least in terms of detergents). By choice of crude raw material or by employing a special adsorptive separation stage, or both, the composition of the resulting OXO alcohols is changed relative to the Shell and Sasol processes and makes them very suitable for the preparation of surfactants, especially for low wash temperatures, Applications requiring high solubility (tight granules, flakes) or high water hardness. All of these have great economic effects. The invention also includes modified primary OXO alcohols prepared by any of the present methods, depending on the compositional variation imparted to the OXO alcohols.

Likewise, the present invention includes consumer oriented cleaning products prepared by the above process comprising the preparation of the particular OXO alcohols described herein, followed by a stage comprising mixing at least one cleaning product additive material component.

In other variations, the process herein includes a method in which the product of said stage (B) or (C) is mixed with conventional detergent olefins prior to said OXO stage (D); or wherein said stage (E ), (F) or (G) are mixed with a conventional detersive surfactant.

Although there are many configurations in which the present process is capable of simultaneously producing modified alkylbenzenes and modified primary OXO alcohols, or alternating process cycles, this non-limiting process according to the invention further comprises at least one stage: The product of stage (A) is reacted with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst; the alkylation catalyst has a selective The internal isomer with a sex of 0-40. Branching involves providing equipment to the product route of stages (C)-(D), the alkylation step, or both stages. See the accompanying drawings for further description.

More broadly, the present invention also includes detergent or cleaner compositions comprising: (a) an effective amount of a detersive surfactant selected from the group consisting of alkyl sulfates, alkyl poly(alkoxy)sulfates Salts, alkyl poly(alkoxides) and mixtures thereof, said surfactants are added to detergent alcohols of formula ROH with R=C9-C20 in the R-O-group (preferably in an amount of up to one mole, more preferably about one mol), wherein R is a mixture of methyl branches and some straight chains, the alcohol is further characterized as containing at least one Fischer-Tropsch process stage or dimerization or skeletal isomerization stage or olefin and/or paraffin Products of the supply stage (e.g. by adsorption separation above or other methods such as hydroisomerization/cracking of waxes, Flexicoking_, Fluidcoking_, etc.) and at least one OXO process stage; provided that in at least one stage preceding the OXO process stage , the presence of an adsorptive separation stage effective to increase the proportion of methyl-branched olefins used as feed to said OXO process stage; and (b) one or more additives that at least partially contribute to enhancing the useful properties of the composition.

Also included herein are detergent or cleaning compositions comprising (a) an effective amount of a dehydrating agent selected from the group consisting of alkyl sulfates, alkyl poly(alkoxy) sulfates, alkyl poly(alkoxides) and mixtures thereof. Detergent surfactants added to detergent alcohols of formula ROH (preferably in an amount of up to one mole, more preferably about one mole) with R=C9-C20 in the R-O- group, wherein R is a methyl branch and certain straight-chain mixtures, said alcohol further characterized as comprising any product of the above-described process for the preparation of modified primary OXO alcohols; and (b) one or more additives which at least in part contribute to improving the useful properties of the composition . Cleaning Product Implementation

Cleaning product embodiments of the present invention include various laundry detergents, dishwashing detergents, hard surface cleaners, and the like. In such embodiments, the modified alkylbenzene sulfonate or the surfactant derived from the modified primary OXO alcohol prepared by the process of the present invention is from about 0.1% to about 99.9%, usually from about 1% to about 50%, and the composition also includes from about 0.1% to about 99.9%, usually from about 1% to about 50%, of various cleaning product additive materials such as co-surfactants, builders, enzymes, bleaching agents, bleaching Accelerators, activators, or catalysts, etc.

The present invention also includes cleaning products prepared by the method of the present invention comprising:

(a) from about 0.1% to about 99.8%, usually up to about 50%, of a modified alkylbenzene sulfonate surfactant as prepared herein or a modified primary OXO alcohol derived surfactant such as a modified alkanol Sulfates, modified poly(alkoxy)sulfates, etc., and

(b) from about 0.00001%, more typically from at least about 1% to about 99.9%, of one or more of the cleaning product additive materials described herein.

Since the range of various additive materials is quite wide, a wide range of amounts can be used. For example, very low or very high (less common) levels of various detergent enzymes such as proteases, amylases, cellulases, lipases, etc. as well as various bleach catalysts (including macrocyclic types with manganese or all similar to transition metals that can be used in laundry and cleaning products).

Other cleaning product additive materials suitable herein include various bleaches, especially oxygen bleaching types, including those activated and catalyzed with such bleach activators, such as nonanoyloxybenzenesulfonate and/or tetraacetylethylene glycol Amines and/or any derivatives thereof or derivatives of various phthalimidopercaproic acids or other imino- or amino-substituted bleach activators (including lactam types), or more generally hydrophilic and/or hydrophobic bleach activators (especially various acyl derivatives, including those types of C6-C16 substituted dobesylates); relating to or based on any of the previously mentioned bleach activators, Various preformed peracids of builders, including insoluble types such as various zeolites including zeolite A, P and so-called maximal aluminum P, and soluble types such as phosphates and polyphosphates, any aqueous, water-soluble or water-insoluble silicate, 2,2'-hydroxydisuccinate, tartrate succinate, glycolate, NTA and many other ether carboxylates or citrates, various chelating agents including EDTA, S, S'EDDS, DTPA and phosphonates, water soluble polymers, copolymers and terpolymers, various soil release polymers, co-surfactants including any known anionic, cationic, nonionic or zwitterionic type, Optical brighteners, various processing aids such as crisping agents and/or fillers, solvents, anti-redeposition agents, silicon/silicon dioxide and other foam inhibitors, hydrotropes, fragrances or pro-perfumes , dyes, photobleaches, thickeners, mono-salts and alkali metal salts such as those based on sodium or potassium, including their hydroxides, carbonates, bicarbonates and sulfates, etc. When mixed with the modified alkylbenzene sulfonate surfactant obtained by the method of the present invention, any anhydrous, water-containing, water-based or solvent-carrying cleaning products are easily made into granules, flakes, powders, flocs, etc. Sheets, gels, extrudates, pouches or sachets, etc. Accordingly, the present invention also includes various cleaning products that may be prepared or produced by any of the methods described. They can be used in discrete doses (by hand or by machine), or they can be fed continuously into all suitable cleaning equipment or delivery devices. Cleaning Product Details

Each reference cited herein is incorporated herein by reference. Surfactant compositions prepared by the process of the present invention can be used in a wide variety of household cleaning product compositions, including powders, granules, gels, pastes, tablets, sachets, sticks, delivery in dual compartment containers Types of spray or foam detergents and other homogeneous and multiphase household cleaning product forms. They can be used or applied by hand, and/or can be administered in consistent or variable doses, or by automatic dispensing devices, or can be used in various appliances such as washing machines or dishwashers, or can be used for cleaning in public establishments Ranges such as personal cleaning in utilities, can be used for bottle washing, for surgical equipment cleaning or for cleaning of electronic components. Its pH range can be very wide, as being about 2-about 12 or higher, and its range of alkali storage capacity also can be very wide (as being used as drain unblocking, wherein every 100 grams of formulas can have the NaOH equivalent of tens of grams, From the amount of 1-10 grams of NaOH to medium or low alkaline liquid hand cleaners to slightly acidic such as acid hard surface cleaners). Includes two types of high suds and low suds detergents.

Various household product cleaning compositions are described in "Surfactant Science Series", Marcel Dekker, New York, Volumes 1-67 and later. Liquid compositions are described in detail in Volume 67, "Liquid Detergents", Ed. Kuo-Yann Lai, 1997, ISBN 0-8247-9391-9 (incorporated herein by reference). More classical formulations (especially granular types) are described in "Production of Detergents Including Other New Materials of Zeolite Builders", Ed. M. Sittig, Noyes Data Corporation, 1979 (incorporated herein by reference ). See also Kirk Othmer's Encyclopedia of Chemical Technology.

The household product cleaning compositions herein include without limitation:

Light Duty Liquid Detergents (LDL): These compositions include LDL compositions having magnesium ions with improved surface activity (see for example WO 97/00930A; GB 2,292,562A; US 5,376,310; US 5,269,974; US 5,230,823; US 4,923,635; US4 , 681,704; US 4,316,824; US 4,133,779) and/or organic diamines and/or various foam stabilizers and/or foam boosters such as amine oxides (see for example US 4,133,779) and/or surfactants, emollients and and/or skin feel improvers of enzyme type including proteases; and/or antimicrobial agents; see Suractant Science Series, Vol. 67, pp. 240-248 for a more comprehensive list of patents.

Heavy Duty Liquid Detergents (HDL): These compositions include so-called "structured" or heterogeneous (see for example US 4,452,717; US 4,526,709; US 4,530,780; US 4,618,446; US 4,793,943; US 4,659,479; US 5,006,273; US 5,021,195; US 5,147,576; US 5,160,655) and "unstructured" or isotropic liquids, and can generally be aqueous or non-aqueous (see for example EP 738,778A; WO 97/00937A ；WO 97/00936A；EP 752,466A；DE 19623623A；WO 96/10073A；WO 96/10072A；US 4,647,393；US 4,648,983；US 4,655,954；US 4,661,280；EP 225,654；US 4,690,771；US 4,744,916；US 4,753,750；US 4,950,424； US 5,004,556; US 5,102,574; WO 94/23009; and may have bleach (see for example US 4,470,919; US 5,250,212; EP 564,250; US 5,264,143; US 5,275,753; US 5,288,746; EP 619,368；US 5,431,848；US 5,445,756)和/或酶(例如参见US3,944,470；US 4,111,855；US 4,261,868；US 4,287,082；US 4,305,837；US 4,404,115；US 4,462,922；US 4,529,5225；US 4,537,706；US4,537,707； US 4,670,179；US 4,842,758；US 4,900,475；US 4,908,150；US 5,082,585；US 5,156,773；WO 92/19709；EP 583,534；EP 583,535；EP 583,536；WO 94/04542；US 5,269,960；EP 633,311；US 5,422,030；US 5,431,842；US 5,442,100) or without bleach and/or enzymes. Other liquid detergents involving heavy-duty types are listed in Surfactant Science Series, Vol. 67, pp. 309-324.

Heavy Duty Granular Detergents (HDG): These compositions include both so called "high density" or agglomerated or non-spray dried and so called "loose" or spray dried. Both phosphated and non-phosphated types are also included. Such detergents may comprise the more common anionic-surfactant-based types or may be of the so-called "high-nonionic" type (wherein nonionic surfactants are usually retained on adsorbed surfaces such as zeolites or other porous inorganic salts in or on the dose). The production of various HDGs is for example disclosed in EP753,571A; WO 96/38531A; US 5,576,285; US 5,573,697; WO 96/34082A; US 5,569,645; 96/25482A; WO 96/23048A; WO 96/22352A; EP 709,449A; WO 96/09370A; US 5,496,487;

Softeners (STW): These compositions include various granules or liquids (see for example EP753,569A; US 4,140,641; US 4,639,321; US 4,751,008; EP 315,126; US 4,844,821; EP 422,787) Softening-through-the wash type products usually have organic (such as quarter) or inorganic (such as clay) softeners.

Hard Surface Cleaners (HSC): These compositions include all-purpose cleaners, such as paste cleaners and all-purpose liquid cleaners; all-purpose spray cleaners, including glass and tile cleaners; and bleach sprays Detergents and all kinds of bathroom cleaners including mildew remover, bleach containing, sterilizing, acidic, neutral and alkaline types. See eg EP 743,280A; EP 743,279A. Acid cleaners include those of WO 96/34938A.

Bar Soaps and Laundry Soaps (BS & HW): These compositions include personal washing bars as well as so-called laundry bars (see for example WO 96/35772A); include synthetic detergent and soap based types and types with softeners (See US 5,500,137 or WO96/01889A); such compositions may include those prepared by various conventional soap-making techniques such as molding and/or more unconventional techniques such as casting, adsorption of surfactants into porous carriers, and the like. Other bar soaps are also included (BR 9502668; WO 96/04361A; WO 96/04360A; US 5,540,852;). Other hand wash detergents include those described in GB 2,292,155A and WO 96/01306A.

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

Liquid Soaps (LS): These compositions include both so-called "antibacterial" and conventional types, as well as those with or without skin conditioning agents, and include types suitable for use in pump dispensers and by other means such as public places Type of wall-mounted unit.

Special purpose cleaners (SPC): including household dry cleaning systems (see for example WO96/30583A; WO 96/30472A; WO 96/30471A; US 5,547,476; WO96/37652A); bleach pretreatment products for laundry (see EP 751,210A); pre-treatment products for the care of fibers (see for example EP 752,469A); liquid fine-fiber detergent types, especially the various types which produce a high suds; rinse aids for dishwashing; various liquid bleaches, Includes both chlorine and oxygen bleaching types, as well as disinfectants, mouthwashes, denture cleaners (see for example WO 96/19563 A; WO 96/19562A), car or carpet cleaners or shampoos (see for example EP 751,213 A; WO 96/15308A), hair rinses, shower gels, foam baths and personal care cleansers (see for example WO 96/37595A; WO 96/37592A; WO 96/37591A; WO 96/37589A; WO 96/37588A ; GB 2,297,975A; GB 2,297,762A; GB 2,297,761A; WO 96/17916A; WO 96/12468A) and metal cleaning agents; and various cleaning aids such as bleaching additives and "dirt adhesion" (stain-stick) or other pre- Types of treatment, including cleaning agents of special foam types (see for example EP 753,560A; EP 753,559A; EP 753,558A; EP753,557A; EP 753,556A), also anti-sunfade treatments (see for example WO 96/03486A; WO 96/03481A ; WO 96/03369A).

Various detergents with long-lasting fragrances (see eg US 5,500,154; WO96/02490) are becoming more common. method combination

The process of the present invention can be integrated in any convenient manner with current LAB production processes or with conventional in-line detergent alcohol processes. For example, conventionally assembled equipment could be entirely converted to produce modified alkylbenzenes and/or modified primary OXO alcohols. Or depending on the required volume or available feedstock (for example as waste liquor from the LAB process or based on similar feedstock sources from the petrochemical industry) for the production of modified alkylbenzenes and/or modified primary The equipment of OXO alcohol can be used as an add-on or supporting equipment in proportion to the existing LAB equipment, or installed as a separate system. The process of the invention can be carried out in both batch and continuous modes of operation.

In a scaled-up mode, the invention involves the preparation of vinylidene olefins and the preparation of modified alkylbenzenes or alkyltoluenes and/or modified primary OXO alcohols using the various steps detailed above. The modified alkylbenzene or alkyltoluene is blended to conventional linear alkylbenzene in a ratio of about 1:100 to 100:1, more preferably about 1:10 to about 10:1 (eg about 1:5) As in the average C11.8 alkylbenzene or any alkylbenzene produced by the ^DETAL_ method. The blend is then sulfonated, neutralized and incorporated into a household cleaning product composition. Parallel process stages or other process stages obtain modified primary OXO alcohols.

The invention should not be limited in scope to the details or examples thereof in the specification, including the examples hereinafter used for illustration. More generally, the present invention shall include any household cleansing composition containing any type of surfactant product wherein the hydrophobe of the surfactant has been modified by a method primarily addressed by the method of the present invention. We believe that this discussion (especially the delinearization method) can be reapplied, for example, in the production of modified alkyl sulfates and other surfactants.

Example 1

The improvement was prepared by separation of a branched hydrocarbon feed from benign carbon/diesel on SAPO-11, dehydrogenation, alkylation on H-mordenite, sulfonation with sulfur trioxide/air and neutralization. Alkylbenzenesulfonate

A suitable brown carbon/diesel distillation cut feed is obtained from kerosene. The feed contains paraffin branched and linear hydrocarbons, wherein the linear hydrocarbons have a chain length suitable for LAB production and wherein the branched hydrocarbons comprise at least about 10% methyl branched paraffins, as well as various cyclic hydrocarbons, aromatics and other impurities. This stream passes continuously through two adsorption separation units connected as shown in Figure 8 and Figure 1 (where unit AC1 of Figure 8 is loaded with 5 Angstrom Ca zeolite as used for conventional linear alkylbenzene production, and unit AC2 of Figure 8 is loaded with There is a silicoaluminophosphate SAPO-11. Units AC1 and AC2 with associated rotary valve arrangements, raffinate and waste columns (RC and EC) and condensers (horizontal tanks not marked as shown in Figure 8) and all The other units shown (albeit connected in a special way) were mainly constructed according to the units ( ^MOLEX_units ) approved and commercially available from UOP Corp. The adsorbate from the Ca zeolite adsorption unit AC1 (extraction material) is discharged, and the effluent is continuously sent to the second adsorption separation unit AC2 containing SAPO-11. The branch-rich stream from unit AC2 as adsorbate or extract is sent to the standard industrial LAB process for desorption Hydrogen unit (supplied by UOP Corp. (PACOL_ method) and loaded with a standard LAB dehydrogenation catalyst (DeH 5_ or DeH 7_ or similar) belonging to UOP Corp.). Under the conditions of various conventional preparative LAB methods After dehydrogenation the hydrocarbons are fed continuously to an alkylation unit which is conventional elsewhere, except that it is loaded with H-mordenite (ZEOCAT_FM 8/25H) in which it is heated at about 200°C Alkylation is carried out continuously at temperature, and discharge when completing at least about 90%, that is, the conversion rate of feed hydrocarbon (olefin) is at least about 90%. Thus obtain modified alkylbenzene. In optional variants , can repeat above-mentioned method, and difference is when the conversion ratio of required modified alkylbenzene reaches at least about 80% (based on olefin) unloading.By carrying out distillation at the rear end of alkylation unit, obtain the paraffin Recycle stream and send this recycle stream back in the dehydrogenation reactor. So far the process includes the steps and streams in Figure 1. Modifications can be made by additional conventional distillation (this distillation step is not shown in Figure 1) Alkylbenzene obtains further purification. Adopt sulfur trioxide as sulfonating agent intermittently or continuously the modified alkylbenzene mixture after distillation is carried out sulfonation (can carry out in different places facility as required). Adopt suitable air/three The details of the sulfonation of the sulfur oxide mixture are described in Chemithon's US 3,427,342. Sodium hydroxide is used to neutralize the modified alkylbenzenesulfonic acid product from the previous step to obtain a modified alkylbenzenesulfonic acid sodium salt mixture.

Example 2

By separating the hydrocarbon feed from Molex_waste on SAPO-11, dehydrogenation using standard UOP method, alkylation on H-mordenite, sulfonation with sulfur trioxide/air and neutralization Preparation of modified alkylbenzene sulfonates

A suitable starting material for waste or raffinate is obtained from a LAB plant, in particular a MOLEX® process unit of such a plant. This raffinate contains a large proportion of branched alkanes as well as various undesirable cyclic hydrocarbons, aromatics and other impurities. This raffinate is fed continuously to an adsorption separation unit of conventional configuration (eg in the manner of a ^MOLEX® unit) but loaded with SAPO-11. This unit was operated under conditions substantially similar to those used for the ^MOLEX® unit for linear alkylbenzene production and similar to unit AC2 described in Example 1. The raffinate or effluent from the SAPO-11 adsorption unit is removed, and the adsorbate or extract meeting the definition of the enriched branch stream of the present invention is continuously sent to a standard industrial LAB process dehydrogenation unit (supplied by UOP Corp. ( PACOL ^_ method) and loaded with UOP Corp. All standard LAB dehydrogenation catalyst (such as DeH 7_)). The continuous feeding of the hydrocarbons after dehydrogenation under the conditions of various conventional methods of preparing LABs is carried out in an otherwise conventional but loaded H-mordenite (ZEOCAT_FM 8/25H) alkylation unit in which the alkanes The alkylation is carried out continuously at a temperature of about 200°C and is discharged when the conversion of the alkylating agent reaches at least about 90%. The modified alkylbenzene mixture is purified by conventional distillation and the branched paraffins are recycled to the dehydrogenation unit. Each step up to here in the method is carried out as shown in FIG. 4 .

Sulfur trioxide is used as a sulfonating agent intermittently or continuously to sulfonate the distilled modified alkylbenzene mixture obtained from the process of the present invention up to here (if necessary, it can be carried out in an off-site facility).

Details of sulfonation using suitable air/sulfur trioxide mixtures are described in US 3,427,342 to Chemithon. Using sodium hydroxide to neutralize the modified alkylbenzenesulfonic acid product in the previous step to obtain a modified alkylbenzenesulfonic acid sodium salt mixture.

Example 3

By separating the hydrocarbon feed from Molex_waste on pyrolyzed poly(1,1-dichloroethylene), dehydrogenation using standard UOP method, alkylation on H-ZSM-12, using Preparation of Modified Alkylbenzene Sulfonates by Sulfur Trioxide/Air Sulfonation and Neutralization

A suitable starting material is obtained in raffinate form from a LAB plant, in particular a ^MOLEX® process unit of such a plant. This raffinate contains branched alkanes as well as cyclic hydrocarbons, aromatics and various other undesirable impurities. This raffinate is continuously fed into an adsorption separation unit of conventional construction (such as the ^MOLEX_ type), but the difference is the introduction of a LAB plant design, hereinafter referred to as " ^SARAN_unit ", loaded with pyrolyzed poly(1, 1-Dichloroethylene), with a sieve diameter greater than 5 Angstroms, manufactured according to Netherlands Application NL7111508 published on October 25, 1971. This "SARAN unit" operates under various conditions similar to the ^MOLEX_unit . The raffinate from the "SARAN unit" was withdrawn and the adsorbate was continuously passed to a standard commercial LAB process dehydrogenation unit (supplied by UOP Corp. ( ^PACOL_ process) and loaded with a standard LAB dehydrogenation catalyst owned by UOP Corp. As in DeH7_). The continuous feeding of the hydrocarbons after dehydrogenation under the conditions of various conventional LAB production processes to an otherwise conventional but H-ZSM-12 loaded alkylation unit where alkylation occurs at about The operation is carried out continuously at a temperature of 200°C, with discharge at a conversion of at least about 90% of the hydrocarbon input. The modified alkylbenzene mixture obtained in the previous step is distilled and sulfonated intermittently or continuously using sulfur trioxide as a sulfonating agent. Details of sulfonation using suitable air/sulfur trioxide mixtures are described in US 3,427,342 to Chemithon. Using sodium hydroxide to neutralize the modified alkylbenzenesulfonic acid product in the previous step to obtain a modified alkylbenzenesulfonic acid sodium salt mixture.

Example 4

Prepared by separation of hydrocarbon feed from urea clathration on SAPO-11, dehydrogenation over Pt catalyst, alkylation over acidic beta-zeolite, sulfonation with sulfur trioxide/air and neutralization Modified alkylbenzene sulfonate

A suitable feedstock is obtained from kerosene by urea clathration (used to remove fractions enriched in more commercially valuable linear hydrocarbons). See US 3,506,569. The lower branch effluent from the urea clathration stage is suitable as hydrocarbon feed to the process of the present invention. It is stripped to remove any activator solvent such as methanol (if present) and fed continuously to an adsorption separation unit configured in any conventional manner (such as in the manner of a ^MOLEX® process unit) except that it is loaded with SAPO-11 middle. The SAPO-11 unit was operated under conditions similar to standard ^MOLEX® handling units. The raffinate from the SAPO-11 unit was withdrawn and the adsorbate was continuously passed into a standard industrial LAB process dehydrogenation unit (supplied by UOP Corp. ( ^PACOL® process) and loaded with a non-proprietary platinum dehydrogenation catalyst). The hydrocarbons are fed continuously after dehydrogenation under the conditions of various conventional LAB production processes to an otherwise conventional, but Zeocat PB/H-loaded alkylation unit in which the alkylation takes place at about The process is carried out continuously at a temperature of 200°C, with discharge at a conversion of at least about 90% of the input hydrocarbons. Using sulfur trioxide as a sulfonating agent to carry out batch or continuous sulfonation of the modified alkylbenzene mixture prepared in the previous step. Details of sulfonation using suitable air/sulfur trioxide mixtures are described in US 3,427,342 to Chemithon. Using sodium hydroxide to neutralize the modified alkylbenzenesulfonic acid product in the previous step to obtain a modified alkylbenzenesulfonic acid sodium salt mixture.

Example 5

By separation of hydrocarbon feeds from kerosene cuts of highly paraffinic petroleum on grafted non-acidic zeolites, dehydrogenation with DeH 9_ catalyst, alkylation on H-mordenite, chlorosulfonic acid Sulfonation and neutralization to prepare modified alkylbenzene sulfonate

Brown carbon/kerosene cuts are obtained from low viscosity crude oils such as Brent light. This is fed continuously to an adsorption separation unit configured in any conventional way (eg in the manner of a ^MOLEX® process unit) but loaded differently (with a grafted zeolite prepared according to US 5,326,928). This unit operates under conditions similar to the ^MOLEX_units of conventional vectors. The raffinate from this unit was drained and the adsorbate was continuously passed into a standard commercial LAB process dehydrogenation unit (supplied by UOP Corp. ( ^PACOL_ process) and loaded with standard LAB dehydrogenation catalyst DeH9_ owned by UOP Corp. . The hydrocarbons are continuously fed to an otherwise conventional but loaded H-mordenite (ZEOCAT FM 8/25H) alkylation unit after dehydrogenation under the conditions of the various conventional methods for preparing LAB, in which The alkylation is carried out continuously at a temperature of about 200°C and is discharged when conversion of the input hydrocarbons reaches at least about 90%. Using sulfur trioxide as a sulfonating agent to carry out batch or continuous sulfonation of the modified alkylbenzene mixture prepared in the previous step. Details of sulfonation using suitable air/sulfur trioxide mixtures are described in US 3,427,342 to Chemithon. Using sodium hydroxide to neutralize the modified alkylbenzenesulfonic acid product in the previous step to obtain a modified alkylbenzenesulfonic acid sodium salt mixture.

Example 6

Composition of cleaning products

10% by weight of the modified alkylbenzene sulfonate sodium salt product of any of the above exemplary processes is mixed with 90% by weight of agglomerated high density laundry detergent granules.

Example 7

Composition of cleaning products

In this example, the following abbreviation is used to represent the modified alkylbenzene sulfonate (in sodium or potassium salt form) prepared according to any of the preceding method examples: MAS.

The following abbreviations are used to represent cleaning product additive materials: _Cxy Amine Oxide Given chain length Cxy Alkyl Dimethylamine Oxide N-oxide

  RN(O)Me2, where the average total carbons of the non-methyl alkyl moiety R

Amylase in the range of 10+x to 10+y sold under the trade name Termamyl 60T by NOVO Industries A/S

Amylolytic enzyme sold with an activity of 60KNU/g. or, from

The following amylases: Fungamyl_; Duramyl_; BAN_ and

Described in WO95/26397 and in Novo Nordisk's joint

Alpha-Amylase APA C8-C10 Amidopropyldimethylamine C _xy Betaine of Decision Application PCT/DK96/00056 Alkyl moiety with average total carbons in the range 10+x to 10+y

Dimethylbetaine bicarbonate Anhydrous sodium bicarbonate, particle size distribution 400μm-1200μm Borax Sodium tetraborate decahydrate BPP Butoxy-propoxy-propanol brightener 1 4,4'-bis(2 -Sulfostyryl) diphenyl disodium brightener 2 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino)

Disodium Stilbene-2,2'-Disulfonate CaCl ₂ Calcium Chloride Carbonate Anhydrous Na ₂ CO ₃ , 200μm-900μm Cellulose Acid Cellulolytic Enzyme, 1000CEVU/g, NOVO ^, Carezyme_Citrate Citrate Trisodium dihydrate, 86.4%, 425 μm-850 μm citrate Citric acid, anhydrous CMC Sodium carboxymethylcellulose C _xy AS Alkyl sulfate, Na salt or other specified salt, alkyl moiety

Average total carbons in the range 10+x to 10+yC _xy E _z Industrial linear or branched alcohol ethoxylates (no intermediate chain

  of the methyl branch of ), with an average of z moles of cyclohexane having an alkyl moiety

The average total carbon of the points ranges from 10+x to 10+yC _xy E _z S Alkyl ethoxylate sulfate Na salt (or other salt), average

Z moles of ethylene oxide have an average total carbon range of alkyl moieties

For 10+x to 10+y diamines Alkyl diamines, such as 1,3-propanediamine, Dytek EP, Dytek

A (Dupont) or selected from: Dimethylaminopropylamine; 1,6-Hexanedi

Amine; 1,3-propylenediamine; 2-methyl-1,5-pentanediamine; 1,3-pentanediamine;

            1-Methyl-diaminopropane; 1,3-cyclohexanediamine; 1,2-cyclohexanedi

Amine Dimethicone 40(Gum)/60(Fluid)(Wt), SE-76 Dimethicone

Gum (G.E Silicones Div.)/Polymer Div. with a viscosity of 350 centistokes

diethylenetriaminepentaacetic acid DTPMP diethylenetriaminepenta(methylenephosphonic acid),

Monsanto (Dequest 2060) endoglucanase Endoglucanase, activity 3000CEVU/g, NOVOEtOH 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 acid (RPS) rapeseed fatty acid fatty acid (TPK) topped palm kernel fatty acid formate formate (sodium) HEDP 1,1-hydroxyethanediphosphonic acid hydrotrope selected from toluenesulfonic acid, Naphthalenesulfonic acid, cumenesulfonic acid, xylene

Sodium, potassium, magnesium, calcium, ammonium salts of sulfonic acids, or water

Soluble substituted ammonium salt Isofol 12 X12 (average) Guerbet alcohol (Condea) Isofol 16 C16 (average) Guerbet alcohol (Condea) LAS linear alkylbenzene sulfonate (such as C11.8, Na or K Salt) lipase lipolytic enzyme, 100kLU/gram, NOVO, ^Lipolase_ , or

A lipase selected from the group consisting of: Amano-P:M1 lipase_;

Lipomax_;D96L - derived as described in US serial number

Natural lipase of Humicola lanuginosa of 08/341,826

Lipolytic enzyme variants; and Humicola lanuginosa strains

DSM 4106LMFAA C12-14 alkyl N-methyl glycosamide MA/AA 1: 4 Malanic acid/acrylic NA salt cluster, the average weight average molecular molecular

The amount is 70,000 MBA _x E _y medium chain branched primary alkyl ethoxylate (average total carbon number = x; flat

Both EO=y) MBA _x E _y S Mid-chain branched or modified primary according to the invention (see Example 9)

Alkyl ethoxylate sulfate (Na salt, average total carbon number = x;

Average EO=Y), MBA _y S medium chain branched primary alkyl sulfate, Na salt (average total carbon number = y) MEA monoethanolamine C _xy MES alkyl methyl ester sulfonate (Na salt) average of the alkyl moiety total carbon range

10+x to 10+y MgCl ₂ magnesium chloride MnCAT macrocyclic manganese bleach catalyst (as in EP 544,440A) or preferably

Use [Mn(Bcyclam)Cl ₂ ], where Bcyclam=5,12-dimethyl

yl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane or as reference

(comparable) bridged tetraazamacrocyclic NaDCC sodium dichloroisocyanurate NaOH sodium hydroxide C _xy NaPS paraffin sulfonate (Na salt), the average total carbon range of the alkyl moiety

10+x to 10+y NaSKS-6 crystalline phyllosilicate of formula δ-Na ₂ Si ₂ O ₅ NaTS sodium toluene sulfonate NOBS nonanoyl oxybenzene sulfonate (sodium salt) LOBS C12 oxybenzene sulfonate (sodium salt) PAA polyacrylic acid (mw=4500) PAE ethoxylated tetraethylene pentamine PAEC methyl quaternized ethoxylated diexene triamine PB1 standard formula is NaBO ₂ ·H ₂ O ₂ anhydrous sodium perborate bleach PEG polyethylene glycol (mw=4600) percarbonate Sodium percarbonate PG propylene glycol photobleach with general formula 2Na ₂ CO ₃ 3H ₂ O ₂ encapsulated (encapsulated) Zinc sulfonate in dextrin soluble polymer

Phthalocyanine PIE Ethoxylated polyethyleneimine protease Proteolytic enzyme, 4KNPU/gram, NOVO, Savinase ^_ or

A protease selected from the group consisting of: Maxatase_; Maxacal_;

  Maxapem 15_; Subtilisin BPN and BPN';

Protease B; Protease A; Protease D; Primase_;

Durazym_; Opticlean_ and Optimase_ and

Alcalase_QAS R ₂ ·N ⁺ (CH ₃ ) _x ((C ₂ H ₄ O) _y H) _z ,R ₂ =C8-C18,x+z=3,

x=0-3,z=0-3,v=1-15C _xy SAS Secondary alkyl sulfate (sodium salt), the average carbon number range of the alkyl part

Silicate from 10+x to 10+y Sodium silicate, amorphous (SiO ₂ :Na ₂ O=2.0) polysiloxane defoamer polydimethylsiloxane foam control agent + silicon as dispersant oxygen

Alkane-oxyalkylene copolymer; foam control agent: dispersant = 10:1-

       100:1; or fumed silica with high viscosity polydimethyl

Conjugation solvents of siloxanes (optionally chemically modified) Non-aqueous solvents such as hexanediol, see also propylene glycol SRP1 Sulfobenzoyl with oxyethyleneoxy and terephthaloyl backbone

Methyl-terminated ester SRP2 Sulfonated ethoxylated terephthalate polymer SRP3 Methyl-terminated ethoxylated terephthalate polymer STPP Sodium tripolyphosphate, anhydrous sulfate sulfuric acid Sodium, anhydrous TAED Tetraacetylethylenediamine TFA C16-18 Alkyl N-methylglucamide Zeolite A Hydrated sodium aluminosilicate, Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ 27H ₂ O; 0.1-10

Typical components commonly referred to as "minor ingredients" for Zeolite (Maximum Aluminum P) Detergent Grade (Crosfield) can include fragrances, dyes, pH adjusters, etc.

The following examples serve to illustrate the invention, but are not meant to limit or define its scope. All parts, percentages and ratios used are by weight unless otherwise indicated. The following laundry detergent compositions AF were prepared according to the present invention: A B C D. E. f MAS twenty two 16.5 11 1-5.5 10-25 5-35 Any combination of: C45 ASC45E1SLASC26 SASC47 NaPSC48 MESMBA16.5SMBA15.5E2S 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 PAAA 2.3 2.3 2.3 2.3 0-5 0-5 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 2ppm 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 SRP1 or SRP2 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 Polysiloxane defoamer 0.42 0.42 0.42 0.42 0-0.5 0-1 Sulfates, water, minor components to 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

Composition of cleaning products

The following liquid laundry detergent compositions AE were prepared according to the present invention. Abbreviations are the same as those used in previous examples. A B C D. E. MAS 1-7 7-12 12-17 17-22 1-35 Any combination of: C25E1.8-2.5SMBA15.5E1.8SMBA15.5SC25 AS (linear to higher 2-alkyl) C47NaPSC26 SASLASC26MES 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 acids (TPK or C12/14) 2 2 2 2 0-14 EtOH 4 4 4 4 0-8 PG 6 6 6 6 0-10 MEAs 1 1 1 1 0-3 NaOH 3 3 3 3 0-7 Hydrotrope 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 SRP2 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 Polysiloxane defoamer 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 dye 0.0013 0.0013 0.0013 0.0013 0-0.003 Moisture / Minor Components The remaining part The remaining part The remaining part The remaining part The remaining part Product pH (10% deionized water solution) 7.7 7.7 7.7 7.7 6-9.5

Example 9

In this example, a branch-rich hydrocarbon stream was prepared and dehydrogenated, carbonylated to produce modified primary OXO alcohols, ethoxylates and sulfates.

Suitable crude hydrocarbon feeds are obtained as lignite/diesel or kerosene cuts. This feed is low in sulfur, nitrogen, and aromatics (which to some extent are believed to negatively impact MOLEX_ and OLEX_ adsorbent beds) and contains paraffinic branched and linear hydrocarbons, where the linear hydrocarbons have properties suitable for scrubbing and wherein the branched hydrocarbons comprise at least about 10% methyl branched paraffins; and cyclic hydrocarbons, aromatics and other impurities.

Distillation of the crude hydrocarbon feed yields a two-carbon cut of about C14-C15. This forms a suitable hydrocarbon feed suitable for the remainder of the process of the invention. See stream 1 in FIG. 10 .

The distilled hydrocarbon feed is fed continuously to two adsorption separation units connected as shown in Figure 10, where unit SOR4/5 is loaded with 5 Angstrom Ca zeolite for conventional linear alkylbenzene production and unit SOR 5/7 is loaded with There is silicoaluminophosphate SAPO-11. Units SOR 4/5 and SOR 5/7 and ancillary equipment not shown in Figure 10 are licensed and available from UOP Corp. (MOLEX_units). Not shown are the adsorbent system and auxiliary distillation and recovery columns. A linear stream rich in Ca zeolite from MOLEX_unit SOR 4/5 (stream 6 in FIG. Branched hydrocarbons) are continuously sent to the second adsorption separation unit SOR 5/7 containing SAPO-11. The branched-rich stream from unit SOR 5/7 as adsorbate and extract (stream 3 in Figure 10, with more branched hydrocarbons) was sent to the standard industrial LAB process (PACOL _ method) dehydrogenation unit (DEH in Figure 10) equipped with a standard dehydrogenation catalyst proprietary by UOP Corp. (DeH 5_ or DeH 7_ or similar). After partial dehydrogenation (up to about 20%) under conventional LAB olefin feed preparation process conditions, the branched olefin/paraffin-rich mixture (stream 4 in Figure 10) is fed continuously to the UOP Corp. Registered DEFINE_ and PEP_ process units. These units hydrogenate diene impurities to mono-olefins and help reduce the level of aromatic impurities. The resulting purified olefin/paraffin stream (54 in Figure 10) is now sent to the OLEX_ process unit registered by UOP, which is equipped with UOP Corp.'s proprietary olefin separation adsorbent. After the olefins have been separated from the unreacted paraffins (the latter being recycled as stream 8 in Figure 10), the branched olefins (stream 55 in Figure 10) are continuously fed to the OXO reaction unit, which operates under the following conditions: A _H2 :CO ratio of 2-2.5:1, a pressure of about 60-90 atmospheres, a temperature of about 170°C to about 210°C, and a cobalt organophosphine complex charged. The OXO treatment is performed continuously while the selectivity to the modified primary OXO alcohol is at least about 90% and substantially all of the olefins in the input stream have reacted. This results in the modified primary OXO alcohols according to the invention. Small amounts of reduced products also form paraffins. Paraffins are separated by the distillation section and can be recycled to the dehydrogenator. This aspect of the process includes the steps and streams of FIG. 10 . The modified primary OXO alcohol (stream 57 in Figure 10) is ethoxylated to an average molar ethylene oxide content. Alternatively, ethoxylation, propoxylation, etc. can use different amounts of alkylene oxides to produce the desired alkoxides. It can be performed batchwise or continuously, if desired, using ethylene oxide and the usual basic catalysts in the removal unit (see Schonfeldt, Surface ActiveEthylene Oxide Adducts, Pergamon Press, NY, 1969). Ethoxylated modified OXO alcohols are now treated in batch or continuous mode with sulfur trioxide as sulfating agent (see "Sulphonation Technology in the Detergent Industry", W. de Groot, Kluwer Academic Publishers, London, 1991). The product of the previous step is neutralized with sodium hydroxide to obtain the modified sodium salt of alkyl ethoxysulfate according to the invention. In a variation of the above example, the alkyl chain length of the hydrocarbon can be varied to produce a modified OXO alcohol-derived surfactant of the desired chain length (used in the formulation examples). In other variations, the modified OXO alcohols can be sulfated without prior alkoxylation.

Example 10

A non-limiting example of the preparation of a non-aqueous liquid laundry detergent containing bleach, the composition of which is shown in the table below:

The score of the table group (weight) range ( %, weight) liquid LAS 25.0 18-35C24E5 or MBA14.3E5 (Example 9) 13.6 10-20 solvent or hex glycol 27.3 20-30 spice 0.4 0-14.4E1S (Example 9) 2.3 1-3.0 solid-phase protease 0.4 0-1.0 Citric acid salt 4.3 3-6PB1 3.4 2-7Nobs 8.0 2-12 carbonate 13.9 5-20dtpa 0.9 0-1.5 bright agent 1 0.4 0-0.6 Polysiloxane defoamer 0.1 0-0.3 Minor component Balance -

The resulting composition is an anhydrous heavy duty liquid laundry detergent which provides excellent soil and stain removal performance when used in normal fabric laundering operations.

Example 11

Liquid detergent compositions are prepared according to the following. A B C D. MBA14.4E1S (embodiment 9) 2 8 7 5 MBA14.4S (embodiment 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 1 1 1 fatty acids (12/18) 11 4 4 3 citric acid 1 3 3 2 DTPMP 1 1 1 0.5 MEAs 8 5 5 2 NaOH 1 2.5 1 1.5 Solvent or PG 14.5 13.1 10.0 8 ethanol 1.8 4.7 5.4 1 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 Endonuclease (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 Hydrotrope - 3 - - Isofol 12 1 1 1 1 Polysiloxane defoamer 0.3 0.3 0.3 0.3 water and minor ingredients to 100%

We have found the above liquid detergent compositions (A-D) to be highly efficient in removing various stains and soils from fabrics under various application conditions.

Example 12

The following compositions (EJ) according to the present invention are heavy duty liquid laundry detergent compositions. Examples# E. f G h I J MBA14.4E0.8S (embodiment 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 acids (C12/C14) 7.5 1.1 2.0 4.0 5.0 5.0 fatty acids (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 Endonuclease 0.1 0.1 - - - - Brightener 2 0.1 0.1 - - - - Borax 3.0 3.0 3.5 3.5 4.0 4.0 MEAs 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 ethanol 1.0 1.0 3.5 3.5 6.0 6.0 Hydrotrope - - 2.5 2.5 - - Secondary ingredient margin margin margin margin margin margin

Example 13

Water-based heavy duty laundry detergent compositions KO containing the mid-chain branched surfactants of the present invention are listed in the table below. Element K L m N o MBA14.4E0.8S (embodiment 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 acids (TPK, RPS or C12/C14) 2 2 2 2 0 PAE 1 1 1.2 1.2 0.5 PG 8 8 8 8 4.5 ethanol 4 4 4 4 2 Borax 3.5 3.5 3.5 3.5 2 Hydrotrope 3 3 2 3 0 pH= 8.0 8.0 8.0 8.0 7.0 water and minor ingredients margin margin margin margin margin 100% 100% 100% 100% 100%

Example 14

According to the present invention, the following aqueous liquid laundry detergent compositions PT were prepared: 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 the following: C25E1.8-2.5SC25AS (linear to high 2-alkyl) C47 NaPSC26 SASLASC26MES 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 1 1 1.5 0.5-2 citric acid 5 5 5 5 0-8 Fatty acids (TPK, RPS or C12/C14) 2 2 2 10 0-14 ethanol 4 4 4 4 0-8 PG 6 6 6 6 0-10 MEAs 1 1 1 1 0-3 NaOH 3 3 3 3 0-7 Hydrotrope 2.5 2 1.5 1 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 SRP2 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 Polysiloxane defoamer 0.12 0.12 0.12 0.12 0-0.3 water and minor components margin margin margin margin margin Product pH (10% in deionized water) 7.7 7.7 7.7 7.7 6-9.5

Example 15

Preparation of light duty liquid dishwashing detergent compositions containing the modified primary OXO alcohol derived surfactants of the present invention: components %wtA % weight B %wtC % weight D MBA13.5E0.6S (embodiment 9) 5 10 20 30 MBA12.5E9 (embodiment 9) 1 1 1 1 C23E1S 25 20 10 0 LMFAA 4 4 4 4 C24 amine oxide 4 4 4 4 EO/PO Block Copolymer-Tetronic_704 0.5 0.5 0.5 0.5 ethanol 6 6 6 6 Hydrotrope (calcium xylene sulfonate) 5 5 5 5 Mg ⁺⁺ (added as chloride) 3.0 3.0 3.0 3.0 water and minor ingredients margin margin margin margin pH@10% (Preparation) 7.5 7.5 7.5 7.5 E. f G h I J pH10% 9.3 8.5 11 10 9 9.2 MBA13.5E0.6S or MBA13.5S (embodiment 9) 10 15 10 27 27 20 C25PS 10 0 0 0 0 0 LAS 5 15 12 0 0 0 C26 betaine 3 1 0 2 2 0 C24 amine oxide 0 0 0 2 5 7 LMFAA 3 0 1 2 0 0 C11E8 0 0 20 1 0 2 Hydrotrope 0 0 0 0 0 5 diamine 1 5 7 2 2 5 Mg ⁺⁺ (in the form of _MgCl2 ) 1 0 0 3 0 0 Ca ⁺⁺ (in the form of 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 minor ingredients to 100%

Example 16

According to the present invention, the following laundry detergent compositions KO were prepared: K L m N o MBA14.4E0.5S (embodiment 9) twenty two 16.5 11 1-5.5 10-25 Any combination of faces: 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 PAAA 2.3 2.3 2.3 2.3 0-5 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 SRP1 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 Polysiloxane defoamer 0.42 0.42 0.42 0.42 0-0.5 water and minor components …margin… Density(g/L) 663 663 663 663 600-700

Example 17

According to the present invention, the following laundry detergent compositions PT were prepared: P Q R S T MBA14.4E0.4S (embodiment 9) 16.5 12.5 8.5 4 1-25 Any combination of faces: 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 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 SRP1 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 Polysiloxane defoamer 0.4 0.4 0.4 0-1 water and minor components …margin… Density(g/L) 850 850 800 850 850

Example 18

According to the present invention, the following high density detergent formulations UX were prepared: u V W x Agglomerates C45AS 11.0 4.0 0 14.0 MBA14.3E0.5S (embodiment 9) 3.0 10.0 17.0 3.0 Zeolite A 15.0 15.0 15.0 10.0 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 (embodiment 9) 5.0 5.0 5.0 5.0 spices 0.5 0.5 0.5 0.5 Additives 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 SRP1 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 Polysiloxane defoamer 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 - Residue (water/various substances) 100 100 100 100 Density (g/l) 850 850 850 850

As illustrated herein, the process can use many different hydrocarbon feeds. Alternative hydrocarbon feeds that may be used in the process include mixtures of certain types of paraffins and/or monoenes. These hydrocarbon mixtures may be selected from:

A． Mixtures of paraffins of the formula:

wherein the total number of carbon atoms in the branched primary alkyl portion of this formula (including the R, ^R and ^R branches) is 8-20, preferably 10-20; preferably about 10 to about 18; R, ^R and ^R Each independently selected from hydrogen, C ₁ -C ₃ alkyl and mixtures thereof and a small proportion of impurities such as C ₃ -C ₇ cycloalkyl, aryl, arylalkyl and alkaryl, preferably H and C _{1 -C3} alkyl (more preferably methyl), with the proviso that R, ^R1 and ^R2 are not all hydrogen and when z is 0, at least R or R1 is not hydrogen; w, x, y, z are each independently Integer of 0-13, the limitation is that the upper limit of the total carbon number and preferably w+x+y+z are 8-14.

More preferably only hydrogen, methyl, ethyl, propyl or butyl are the only alkanes on R, ^R1 and ^R2 , even more preferably only hydrogen and methyl, with the proviso that R, ^R1 and ^R2 include at least one alkane and when a methyl group is present, it is preferably an internal methyl group, that is to say as much as possible is removed from the 1-, 2- or even 3-carbon position of the longest countable chain.

Hydrocarbons here also include:

B． monoene mixture. These monoenes are related to the above paraffin A: the appropriate monoene can be prepared by dehydrogenating the above paraffin. (It is actually possible to isolate suitable alkenes first and then hydrogenate them to paraffins). Preferred olefins are monoolefins, although typically up to about 10% by weight of the olefins may be diolefins after dehydrogenation of suitable paraffins.

或 Like alkanes, the alkenes here can undergo large structural changes, such as possible monoenes:

or

These structures are of course schematic and not restrictive.

Hydrocarbons here also include:

C． Mixture of alkanes A and alkenes B

These hydrocarbon mixtures here may exist in any possible combination and may be compositions such as paraffins alone, olefins alone or a mixture of paraffins/olefins in any ratio. The mixture may itself be derived from hydrocarbons of natural origin such as mineral crude oil (e.g. light crude oil or kerosene or lignite/diesel fuel distilled therefrom), usually by subjecting these materials to some processing (e.g. by fractional distillation, selective adsorption, distillation, clathration, etc.) to separate the preferred hydrocarbon mixture. Alternatively, the mixture may be prepared by stepwise blending more complex mixtures from a series of compositionally simple hydrocarbons. The hydrocarbon mixtures of the present invention may also be derived from synthetic transformations known in petrochemistry, such as cracking, hydrocracking, hydroisomerization, hydrogenation, dimerization, dehydrogenation, isomerization, disproportionation, and the like. Alternatively, comparable compositions can be obtained with more painstaking efforts by known organic synthesis protocols such as those involving Grignard reactions. Catalytic isomerization over zeolites and modified zeolites is especially advantageous.

The hydrocarbon mixture here may further include:

D． mixtures of alkenes A and alkenes B and other known alkenes and/or alkanes (especially linear) having the same or less preferably different carbon number ranges;

Hydrocarbons here also include:

E． Mixtures of A-D with benzene or other non-aliphatic hydrocarbons. It includes the use of other solvents such as cyclohexane, pentane, toluene, and the like.

(Ⅲ)

One class of preferred paraffins has the formula selected from: (II)

(Ⅲ)

Or a mixture thereof; wherein a, b, d and e are integers, a+b is 10-16, and d+e is 8-14, wherein further:

When a+b=10, a is an integer of 2-5, b is an integer of 5-8;

When a+b=11, a is an integer of 2-5, b is an integer of 6-9;

When a+b=12, a is an integer of 2-6, b is an integer of 6-10;

When a+b=13, a is an integer of 2-6, b is an integer of 7-11;

When a+b=14, a is an integer of 2-7, b is an integer of 7-12;

When a+b=15, a is an integer of 2-7, b is an integer of 8-13;

When a+b=16, a is an integer of 2-8, b is an integer of 8-14;

When d+e=8, d is an integer of 2-7, and e is an integer of 1-6;

When d+e=9, d is an integer of 2-8, and e is an integer of 1-7;

When d+e=10, d is an integer of 2-9, and e is an integer of 1-8;

When d+e=11, d is an integer of 2-10, and e is an integer of 1-9;

When d+e=12, d is an integer of 2-11, and e is an integer of 1-10;

When d+e=13, d is an integer of 2-12, and e is an integer of 1-11;

When d+e=14, d is an integer of 2-13, and e is an integer of 1-12;

The hydrocarbon compositions of the present invention can contain varying amounts of impurities (e.g., up to about 20%, preferably less than about 1%), such as the presence of one or more ether or alcohol oxygen atoms or interrupted carbon chains (so-called "oxidized" impurities). ) or impurities in which, for example, aryl, arylalkyl, or alkaryl moieties are attached to carbon chains as branched chains, or in which quaternary carbon atoms or dienes are present, or in which non-hydrogen moieties are attached to adjacent carbon chains Atomically linked impurities. These impurities are certainly not what we need. It is especially preferred to limit impurities known to have a negative effect on biodegradation or to generate malodors. For maximum mass effect, a smaller fraction of the total carbon is placed on any side chain, with the proviso that the resulting hydrocarbon preferably also has at least one carbon atom on one side chain. The paraffins and/or olefins preferred herein may contain varying amounts of non-alkylbenzene aromatic, cycloalkyl and alkylcycloalkyl impurities, although these more desirably are removed (eg by known adsorption steps). The preferred paraffins and/or olefins here may contain some sulfur and/or nitrogen, but they can generate unpleasant odors and for this or other reasons are preferably removed by desulfurization and/or denitrogenation techniques known in petrochemistry they.

Preferred alkenes are closely related to the above paraffins: they have structures formed by dehydrogenation of any paraffin at an accessible site to form the corresponding monoene. Especially preferred olefins are monomethyl branched and dimethyl branched, especially monomethyl branched olefins.

It should be understood and appreciated that the underlined concept for how to choose the preferred alkanes and alkenes to obtain the best results here involves several features:

(a) Precise selection of mixtures of C ₁₀ -C ₁₈ hydrocarbons generally having one or two alkyl substituents, preferably as short as possible and located at least in a position to avoid biodegradation. The hydrocarbons of the present invention are thus significantly different from tetrapropylene-type hydrocarbons which are very poorly biodegradable; and

(b) preferably have at least some methyl moieties which are not located in the 2-position of the longest hydrocarbon chain.

Without wishing to be bound by theory, we believe that more complex mixtures within the defined range are especially advantageous in forming hydrophobes with high solubility hardness tolerance, cold water tolerant "modified" surfactants including alkylbenzenes and OXO alcohols .

In addition, these hydrocarbon mixtures can be widely used in the production of modified surfactants. They can be used to prepare modified alkyl sulfates, alkyl alkoxides, alkyl alkoxy sulfates, or alkylaryl sulfonates such as alkylbenzene sulfonates. Alkyl sulfates are prepared first by converting a hydrocarbon mixture into the corresponding alcohol and then optionally sulfating and/or alkoxylating the alcohol. The alcohols can be prepared by any conventional means such as the OXO process. Sulfation and/alkoxylation can likewise be carried out in a conventional manner. Alkylbenzene sulfonates are formed by alkylating benzene with an olefin and then sulfonating the resulting alkylbenzene. The alkylbenzenes formed are so-called "modified alkylbenzene sulfonates".

Claims (24)

1. method comprises:

(A) stage: stage to the small part of hydrocarbon charging that will contain the ramose aliphatic hydrocrbon of 8-20 carbon atom is separated into

-ratio at least a of having improved branch's open-chain hydrocarbons with respect to described hydrocarbon charging is rich in the ramose logistics and chooses any one kind of them or multiple:

-ratio a kind of of having improved linear aliphatic hydrocrbon with respect to described hydrocarbon charging is rich in linear logistics,

-wherein said stage of discharging current (A) of containing ring-type and/or aromatics and/or ethyl or high branch hydrocarbon comprising:

-described hydrocarbon charging is provided; With

-adopt the described charging of porous medium fractionation by adsorption to become described logistics; The described stage (A) adopts and to comprise following both simulated moving bed adsorption tripping device:

-at least one loads the bed of described porous medium; With

-be used for simulating and equipment in the described porous medium motion of the hydrocarbon stream adverse current of described bed;

(B) (ⅰ) make the ramose logistics that is rich in stage (A) form thus to the small part dehydrogenation and comprise

The olefinic of monoene is rich in affluent-dividing, one of optional back or multinomial

(ⅱ) handle described olefinic be rich in affluent-dividing with reduce wherein the diene foreign matter content and

(ⅲ) handle described olefinic and be rich in affluent-dividing to reduce wherein aromatic impurities content;

(C) optional, adsorption separation device by adopt using sorbent material or porous medium partial concentration stage (B) described olefinic at least is rich in affluent-dividing, condition is that described sorbent material or porous medium are different from the porous medium in stage (A) and are suitable for the olefin/paraff iotan separation, and optional endless chain alkane simultaneously is to described dehydrogenation stage (B); With

(D) in the presence of the OXO catalyzer, make the described olefinic that generates in the stage (B) be rich in affluent-dividing or optional further spissated olefinic stream and carbon monoxide and H-H reaction in the stage (C), form the one-level OXO alcohol of modification thus.

2. according to the method for claim 1, satisfy at least one in following the requirement:

The device in described stage (A) comprise one, two or more described equipment and at least two described beds, at least one comprise described porous medium described bed, not being both of the porous medium content of described porous medium and another described bed increased the ability that reservation methyl ramose does not have cycloaliphatic hydrocarbon; With

The described stage (D) is an OXO stage in step, and wherein said OXO catalyzer is the non-iron transition metal of phosphine coordinate.

3. according to the method for claim 2, wherein at least one described bed comprises that routine is used for the porous medium that linear alkyl benzene is produced; Described at least one that is connected to described method is suitable for improving methyl-ramose to small part does not have the ratio of cycloaliphatic hydrocarbon in the logistics in the described stage (B) that is delivered to described method, and be suitable for reducing the ratio of the linear no cycloaliphatic hydrocarbon in the described stage (B) that is delivered to described method, at least partly be removed as the described form that is rich in linear logistics in linear no cycloaliphatic hydrocarbon described in the described stage (A) to small part.

4. according to the method for claim 3, wherein comprise at simulated moving bed adsorption tripping device described in the described stage (A):

-one described equipment, condition are that described equipment can be simulated described porous medium at least two described motions at least one; Or

-at least two described equipment.

5. according to the method for claim 4, two described at least one beds are wherein arranged, each comprises the different described porous mediums of forming, each described at least one bed is controlled by a described equipment, and each described equipment is minimum has eight apertures and be used for obtaining simulating described porous medium in described at least one motion.

6. according to the method for claim 4, wherein saidly is rich in linear logistics and is present in the described stage (A), and the described stage (A) comprising:

(A-ⅰ) is that described linear logistics and the intermediary of being rich in is rich in the ramose logistics and discharges the described linear logistics that is rich in by a described simulated moving bed adsorption tripping device with described hydrocarbon charging fractionation by adsorption; Then

(A-ⅱ) is rich in ramose logistics fractionation by adsorption by another described simulated moving bed adsorption tripping device with described intermediary is to comprise that the described intermediary that does not have the cycloaliphatic hydrocarbon ratio and increase with respect to its branch for described intermediary is rich in the ramose logistics is rich in the ramose logistics and comprises with respect to described and be rich in for the ramose logistics the described discharge logistics that ring-type at least and/or aromatic hydrocarbon ratio increase.

7. according to the method for claim 2, wherein all described beds comprise the unconventional porous medium that is used to produce linear alkylbenzene; The pore size that is connected to the described porous medium of described method is suitable for being delivered to the methyl branch in the logistics in described stage (B) of described method and the ratio of linear no cycloaliphatic hydrocarbon to the small part increase, with reduce ring-type, aromatics and/or the ethyl branch in the described stage (B) be delivered to described method or the ratio of more senior ramose aliphatic hydrocrbon to small part, be not that described linear and described hydrocarbon to the form of small part with the discharging current in the stage (A) methyl branch hydrocarbon is removed.

8. according to the method for claim 3, wherein said hydrocarbon charging comprises that at least 10% methyl ramose molecular weight is at least 128 and be not more than 282 paraffinic hydrocarbons.

9. according to the method for claim 3, wherein have distilation steps before in the stage (D), described thus distillation generates described olefinic and is rich in the affluent-dividing at C ₁₀-C ₁₇The narrower cut that is not more than 3 carbon atoms (preferably being not more than 2 carbon atoms) of scope.

10. according to the method for claim 9, make described hydrocarbon charging or described olefinic be rich in the ramose logistics thus and enter described distilation steps.

11. according to the method for claim 3, wherein said hydrocarbon starting material are the fractionation by adsorption raffinate that derives from linear alkyl benzene preparation method or conventional linear detergent alcohol method.

12., have and be selected from other following step or sequenced each step according to the method for claim 3:

(E) product of sulfation and neutralization described stage (D);

(F) product in described stage of alkoxide (D); With

(G) product in described stage of alkoxide, sulfation and neutralization (D).

13., have another step (H): the product of preceding step is mixed with one or more cleaning product additive materials according to the method for claim 12; Form the cleaning product thus.

14. modification one-level OXO alcohol according to the preparation of the method for claim 1.

15. life cleaning product comprises the tensio-active agent of producing by according to the method for claim 12, the step of mixing at least a cleaning product additive material then.

16. according to the process of claim 1 wherein the described OXO stage (D) before, described stage (B) or product (C) mix with conventional washing composition alkene.

17. according to the method for claim 12, wherein said stage (E), (F) or (G) in the product in arbitrary stage mix with conventional detersive surfactant.

18., further comprise at least one stage: in the presence of alkylation catalyst, make the product and the aromatic hydrocarbon reaction that is selected from benzene, toluene and composition thereof in stage (B) according to the method for claim 1.

19. according to the method for claim 18, the internal (position) isomer selectivity of wherein said alkylation catalyst is 0-40.

20. according to the method for claim 18, wherein generator by stage (C) lead-in stage (D), or imports described alkylation step with product, or described two stages of parallel importing.

21. the product of claim 12.

22. washing composition or cleanser compositions comprise:

(a) be selected from the detersive surfactant of following significant quantity: alkyl-sulphate, poly-(alkoxyl group) vitriol of alkyl, alkyl poly-(alkoxide) and composition thereof, described tensio-active agent adds the detergent alcohol of the formula ROH of R=C9-C20 in the R-O group, wherein R is the mixture of methyl branch and some linear chains, and the further feature of described alcohol is: it comprises that at least a Fischer-Tropsch operation stage or oligomerization or dimerization reaction or skeletal isomerization stage or paraffinic hydrocarbons provide the product of stage and at least one OXO operation stage; Thereby condition is to exist the fractionation by adsorption stage to increase ratio as the methyl branch alkene of described OXO operation stage charging effectively at least one stage before described OXO operation stage; With

(b) one or more help the additive of composition useful quality to small part.

23. according to the washing composition or the cleanser compositions of claim 22, wherein R is selected from the mixture of medium chain methyl branch or some linear chains.

24. washing composition or cleaning compositions comprise:

(a) significant quantity be selected from following detersive surfactant: alkyl-sulphate, poly-(alkoxyl group) vitriol of alkyl, alkyl poly-(alkoxide) and composition thereof, described tensio-active agent adds the detergent alcohol of the formula ROH of R=C9-C20 in the R-O group, wherein R is the mixture of methyl branch and some linear chains, and the further feature of described alcohol is that it comprises product according to the method for claim 1; With

(b) one or more help the additive of the useful quality of composition to small part.

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