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

Prepare improving one's methods of tensio-active agent and product thereof by fractionation by adsorption

Field of the present invention

The present invention relates to can be used for the preparation method of the various tensio-active agents of cleaning product.Preferable methods comprises the various special devices of employing, and the specific combination of taking various fractionation by adsorption steps is to separate some hydrocarbon.Preferred these devices comprise the various combinations of the turning valve of two or more special adsorption bed and two or more specific type and the porous adsorbent of various specific types (its aperture surpasses the aperture of the sorbent material that is used for conventional linear alkyl benzene production).Preferable methods is also used has the optionally special alkylation step of special internal (position) isomer, or special OXO reactions steps.The present invention also relates to the product (alkylbenzene that comprises some modification), alkylbenzenesulfonatsurfactants surfactants, detergent alcohol of these methods and deutero-tensio-active agent and life cleaning product (the various detergent for washing clothess that particularly contain these products) thus.Preferred methods herein adopts the unconventional order of fractionation by adsorption step to guarantee to obtain some ramose hydrocarbon part, these parts are used further to prepare in the other processing step of the useful tensio-active agent of aromatic hydrocarbons or other preparation as alkylating agent then, thereby as OXO reaction formation special detergent alcohol, alkylation subsequently, sulfation or similar step.Surprisingly, these parts even can derive from the waste liquid that is produced in the production of present linear alkyl benzene.

Background of the present invention

Various hyperbranched alkyl benzene sulfonate surfactants once were used for washing composition in the past as those tensio-active agents based on tetrapropylene (being called " ABS " or " TPBS ").Yet we find suitable poor of the biodegradability of these tensio-active agents.An ensuing segment length in the time people improving the production method of alkylbenzene sulfonate so that make it be linear (" LAS ") in practice as much as possible always.The major portion of producing most of technology of linear alkyl benzene sulfonate surfactant all relates to this target.Today, all relate to the linear alkyl benzene sulfonate in the production method of the employed large-scale industry alkylbenzene sulfonate of the U.S..But the linear alkyl benzene sulfonate is not have limitation, for example, and will be more welcome if improve its performance that is used for the hard water cleaning.

People have developed the whole bag of tricks in petroleum industry recently, as the various methods that are used to produce low-viscosity oil or stop bracket gasoline, how these of inventors makes various hydrocarbon go linearizing (delinearize) effect to reach one to have limitation and in check degree to provide to see brand-new useful understanding if being found to be.But this linearizing effect of discussing of going not is to be the feature of the various commercial runs of different field of the current production alkyl benzene sulfonate surfactant that is used for daily necessities.From not relating to the linearizing effect according to telling about the preparation linear compound the LAS tensio-active agent field in a large number, thereby this point is no wonder.

The commercial run that major part is used to prepare various alkylbenzenes depends on the HF or the aluminum chloride-catalyzed alkylating of benzene.It is found that not long ago that some zeolite catalyst can be used in the alkylating of benzene and alkene.A kind of processing step is like this seen the document that is set forth in other ordinary method that is used for producing linear alkylbenzene sulfonate.For example, the DETAL of UOP ^_Method has been used zeolite alkylated catalyst.We believe, DETAL ^_All various commercial runs that are used for alkylbenzene sulfonate production now of method and other can't satisfy preferable methods of the present invention and after this defined alkylation catalyst for optionally requirement of internal (position) isomer.In addition, we also believe DETAL ^_Method catalyzer (or various catalyzer) does not have the medium acidity and the medium pore size of the alkylation catalyst that is used for the preferred process of the present invention.Recently other document description the use mordenite as alkylation catalyst, even but so open combination that various specific process step required for the present invention all can't be provided.In addition, in view of required linearity in the alkyl benzene sulphonate (ABS) product salt of conventional currently known methods, they also comprise relating to usually before carrying out alkylating provides or prepares the various steps that are linear basically rather than remove linearizing hydrocarbon.Other possible exception sees and is set forth in US 5,026,933 and US 4,990,718 in.Angle from detergent industry, these and other known method exists a large amount of limitation and limited aspects such as (mixtures that comprises available various chain lengths) of product compositing range of the distillation fraction of removing or non-washing purposes material of needing to have a large amount of shortcomings in oligomeric acrylamideization or dimerizing olefins with regard to cost, catalyzer in the stage.In brief, from the angle of the professional formulator of Betengent product, these are not to be best by the obtained progress of petroleum industry.

The specific adsorption separating method of employing known in the art is used to prepare linear alkyl benzene (referring to US 2,985,589).But described so far these methods can't obtain the ramose alkylbenzene sulfonate.

Known in the art by comprising the urea clathration and on " molecular sieve ", carrying out the various long-chain methyl paraffinic hydrocarbonss of isolating prepared in various methods as industrial solvent.Referring to ChemicalAbstracts, 83:100693 and JP 49046124 B4.This method it is said and relate to two urea additions, for example adopt urea handle earlier the oil part once with remove as title complex just-alkane, adopt for the second time then excessive urea obtain blended just-adducts of alkane and long-chain monomethyl alkane hydrocarbon.Though this method may have some limited operabilities and generally speaking can be included in total method of the present invention, its limitation is significant.Although this method was come out in 1974, also not can be incorporated into any total method that is used for preparing various tensio-active agents (modified alkylbenzene sulfonates as described here) so far.

As after this background technology part will further describe, it also is well-known how preparing the pure and mild tensio-active agent for preparing thus of various OXO.Yet, the OXO alcohol that provides at present has some shortcomings, as when producing tensio-active agent, be lower than the required solvability of growing cold washing in the solvability of given chain length, perhaps rely on oligomeric, the isomerization and the disproportionation reaction of expensive method such as alkene; The linear material that perhaps still has high level.

Background technology

Following document can be used as 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 4,904,612,4B4 12/07/74; EP 803,561 A2 10/29/97, EP 559,510 A 9/8/93; EP 559, and 51,0B1 1/24/96; US 5,026, and 933; US 4,990, and 718; US 4,301, and 316; US 4,301, and 317; US 4,855, and 527; US 4,870, and 038; US 2,477, and 382; EP 466,558, and 1/15/92; EP469,940,2/5/92; FR 2,697, and 246,4/29/94; SU 793,972, and 1/7/81; US2,564,072; US 3,196, and 174; US 3,238, and 249; US 3,355, and 484; US 3,442, and 964; US 3,492, and 364; US 4,959, and 491; WO 88/07030,9/25/90; US 4,962, and 256; US 5,196, and 624; US 5,196, and 625; EP 364,012 B, 2/15/90; US 3,312, and 745; US 3,341, and 614; US 3,442, and 965; US 3,674, and 885; US 4,447, and 664; US4,533,651; US 4,587, and 374; US 4,996, and 386; US 5,210, and 060; US 5,510, and 306; WO 95/17961,7/6/95; WO 95/18084; US 5,510, and 306; US 5,087, and 788; US 4,301, and 316; US 4,301, and 317; US 4,855, and 527; US 4,870, and 038; US5,026,933; US 5,625, and 105 and US 4,973,788.EP 559 in the document of being quoted from, and 510A and B are particularly related to by logistics being circulated to the high-octane gasoline of preparation in the isomerization reactor.The grafting porous material of EP 559,510 and the grafting of zeolite (as passing through tin alkyl) can be used among the present invention.US 5,107, and 052 relates to the octane value that improves gasoline equally, and describe and adopt various molecular sieves such as AIPO4-5, SSZ-24, MgAPO-5 and/or contain the MAPSO-5 separation of C 4-C6 methyl paraffinic hydrocarbons that is lower than 2% water.It is said these molecular sieves alternative absorption dimethyl paraffinic hydrocarbons and do not adsorb monomethyl and n-paraffin.

People have looked back the production method of alkyl benzene sulfonate surfactant recently.Referring to the 56th volume in " Surfactant Science " series, Marcel Dekker, New York, 1996, specifically comprise the chapter 2 that themes as " alkylaryl sulphonate: history, production; analyze and environmental properties ", in the 39-108 page or leaf, these chapters and sections comprise 297 pieces of reference.This this works provides the reference of a large amount of description the whole bag of tricks and processing step such as dehydrogenation reaction, alkylating, alkylbenzene distillation etc.Also with reference to " Detergent Alkylate " among the Encyclopedia of ChemicalProcessing and Design, Eds.Mc.Ketta andCunningham, Marcel Dekker, N.Y., nineteen eighty-two is specifically at the 266-284 page or leaf.Various adsorption methods such as UOP ' the s Sorbex method method relevant with other are also seen the Encyclopedia of Chemical Technology that is set forth in KirkOthmer, the 4th edition, volume 1 referring to " absorption and liquid separation ", comprises 583-598 page or leaf and the reference of wherein being quoted from.Also referring to the various publications of UOP Corp., comprising can be from UOP Corp., DesPlaines, " the Processing Guide " that obtains among the Illinois simultaneously.The employing molecular sieve carries out industrial paraffinic hydrocarbons segregation and isolating method comprises MOLEX ^_The liquid phase method of (UOP Inc.) and ISOSIV (Union Carbide Corp.) and ENSORB ^_The vapour phase processes of (Exxon Corp.) and TSF_ or Texaco Selective Finishing method.Believe that all these methods all adopt 5 dust molecular sieves as porous medium.NM herein service temperature, pressure and other operational condition and the equipment that is used for any processing step is conventional, that is to say in producing the document of linear alkyl benzene sulfonate surfactant as everyone knows and define those.Each document entire chapter is incorporated this paper by reference into herein.

The US 3,732,325 that is issued on May 8th, 1973 has described the method for fractionation by adsorption aromatic hydrocarbon.

Be issued to purpose US 3,455,815 July 15 in 1969, be issued to the US 3 on December 13rd, 1966,291,726, be issued to 3,201 of August 17 nineteen sixty-five, 491 and be issued to the US 2,985,589 on May 23rd, 1961 and described the simulation moving-bed adsorption separating method that is used for hydro carbons.

The WO 98/23566 (being incorporated herein by reference at this) that is issued to the US 5,780,694 on July 14th, 1998 and is issued on June 4th, 1998 relates to some side chain detergent alcohol and by its deutero-tensio-active agent.These documents comprise well-known OXO method and are applicable to the description of the catalyzer of carbonylation.Specifically referring to 694 pages the 10th and 11 section.

The US 5,510,564 (incorporating into for referencial use at this) that is issued on April 23rd, 1998 is at the purifying hydro carbons, is described aspect the removing of aromatics especially.

The US 5,276,231 that is issued on January 4th, 1994 has described by the tetramethylene sulfone extraction and has removed aromatic substance from hydro carbons.

The US 4,184,943 that is issued on January 22nd, 1980 has described the separation of adsorbed hydrocarbons.

The US 4,006,197 that is issued on February 1st, 1977 has described the adsorbed hydrocarbons separation of normal paraffin.

The US 5,171,923 that is issued to the US 5,220,099 on June 15th, 1993 and is issued on December 15th, 1992 has described by magnesium Y or Na-X zeolite adsorption and has removed aromatic substance, sulfur-bearing, nitrogenous and oxygen containing compound and coloured entity.

In Surfactant Science series, the 7th volume, " anion surfactant " part 1, Marcel Dekker, N.Y., Ed.W.Linfield, 1976, the 2nd chapter " Petroleum-Based Raw Materials for Anionic Surfactants ", the 11-86 page or leaf provides the total background that comprises OXO method (referring to the 71st page and back) and some charging (referring to the 60th page and back).It should be noted that the reference that this part is " branched-chain alkene " at the 65th page of title with the back does not have description to be applicable to that branched-chain alkene-determined " side chain " alkene of method of the present invention is to be unsuitable for biological " firmly " type.Can be " side chain " and linear aldehyde and/or alcohol at the 72nd page with linear conversion of olefines with the described OXO method in back.In addition, this usage of term " side chain " is different from method of the present invention and is taken to the main branch of methyl ramose charging conduct source on the small part intermediate chain, OXO reaction herein provides special methyl branch primary alconol, and wherein having only any ramose second aspect is to come from the OXO reaction.

Just UOPOLEX has been described respectively at above-mentioned reference and the reference wherein quoted ^_Method and used sorbent material in this, referring to as mention the 60-63 page or leaf of the zeolite of doped with Cu or Ag.More detailed content is referring to the US3 that is issued on July 13rd, 1976,969,276 (carrying out adulterated X type or y-type zeolite with silver).Also can be referring to the Hydrocarbon Process of D.B.Broughton and R.C.Berg, the 48th volume (6), 115 (1969); D.B.Broughton and R.C.Berg be at National Petroleum Refiners Association, 1969 can (on March 23rd, 1969) technical report AM-69-38; D.B.Broughton and R.C.Berg are Chemical Engineering (on January 26th, 1970) the 86th page (exercise question is " two kinds of methods of the linear monoolefine of collaborative preparation ").

The 4th edition of Kirk Othmer ' s Encyclopedia of Chemical Technology, (exercise question is " alcohol, a higher aliphatic compound " to the 893-913 page or leaf (1991) of the 1st volume, subtitle is " synthetic method ") describe OXO reaction and formed detergent alcohol, specifically referring to " cobalt catalyst of modification, a step low-pressure process " (904-906 page or leaf).Be noted that once more illustrated methyl branch's alcohol (referring to as the 904th page) can only be generated by linear precursor, and OXO-branch is positioned at 2-position (as above mentioned reference).

Also referring to Surfactant Science series, the 56th volume " anion surfactant " (Marcel Dekker, N.Y., Ed.W.Linfield, 1996, the 1-142 page or leaf that chapter 1 " is used for nonionogenic tenside synthetic raw material " adds as a reference at this) charging that is usually used in production of detergents also described, described and be used for absorption and other isolating currently known methods, described the alkylation of washing composition and described OXO or carbonylation method step (referring to as the 23-25 page or leaf).

The document of OXO method also comprises " adopting the new synthetic of carbon monoxide " (Ed.J.Falbe, Springer-Verlag, New York, 1980).

The industrial method that is different from the preparing washing agent alcohol that can obtain herein should be understood to comprise following order now: isolate linear paraffinic hydrocarbons by fractionation by adsorption from kerosene, pass through PACOL ^_Method (or similar approach) dehydrogenation becomes linear internal olefin, by OLEX_ method (or similar approach) and OXO reaction, (the OXO catalyzer by routine obtains primary alconol such as ENI ' the s LIAL_ alcohol that the 2-alkyl replaces in a kind of mode in two kinds of methods, perhaps with olefin isomerization to terminal position, carry out terminal OXO addition (as the Shell/Mitsubishi method) subsequently) from alkane separation alkene.

Also referring to WO 97/01521A1 that is disclosed on January 16th, 1997 and 95 ZA-0005405 that are disclosed in June 25 nineteen ninety-five.Also announce and disclose, particularly the known OXO alcohol that maybe can supply that maybe can prepare by the OXO method preparation that belongs to these companies referring to the various technology of South Africa Sasol and/or Sastech.

The accompanying drawing summary

Fig. 1-the 18th is according to the synoptic diagram of certain methods of the present invention.Fig. 8 more clearly illustrates the structure of two adsorption separation unit, and each is respectively the type seen in first two steps fractionation by adsorption step of Fig. 1 and Fig. 2.The connection of noticing Fig. 8 is as shown in Fig. 1, but is different from shown in Fig. 2 those.

Solid line is used for representing main processing step and processing stream.Dotted line is illustrated in the whole bag of tricks may be unnecessary but be present in step and logistics in the various preferred implementation of processes schemes.Round rectangle is represented each processing step, stage or unit.Each line that has numeral is represented charging, pilot process stream and product." SOR " expression fractionation by adsorption step." 4/5 " expression adopts small-bore zeolite, particularly Ca zeolite 5A (quite commonly used in linear alkylbenzene is produced) to carry out fractionation by adsorption." 5/7 " expression adopts each porous material such as SAPO-11 or any equivalent porous material with ability of the following various materials of absorption to carry out fractionation by adsorption:

Monomethyl ramose paraffinic hydrocarbons and/or

Monomethyl ramose one alkene and/or

Non-gem-dimethyl paraffinic hydrocarbons and/or

Non-gem-dimethyl alkene

But get rid of the gem-dimethyl hydrocarbon, the hydrocarbon of the ring-type ring of bigger numeral (five, six or) or the hydrocarbon (no matter being aromatic hydrocarbon or aliphatic hydrocrbon) of higher branch degree.Term used herein " gem-dimethyl " refers to have two methyl and is connected on the interior carbon atom of hydrocarbon, as:

Having only absorption phase SOR 4/5 and/or absorption phase SOR 5/7 herein is the type that is used for the stage (a) or the stage (A) that modification one-level OXO alcohol prepares of modified alkylbenzene preparation as described below.

Wide-aperture herein porous material should not adsorb such hydrocarbon.The following various hydrocarbon of phase reaction absorption.Below illustrate the implication of term " non-gem-dimethyl " hydrocarbon indication:

Attention is not in any methyl moiety of main chain end is included the definition of " non-gem-dimethyl " used herein in.In addition, consistent with this regulation, it is adsorbed that following hydrocarbon should be the wide aperture porous material.It is " monomethyl " hydrocarbon:

Be applicable to that herein wide aperture porous material will do more abundant and more fully describe in specification sheets after this." DEH " refers to that the step of part dehydrogenation (the part dehydrogenation is common in the linear alkyl benzene production of routine, though also can adopt complete dehydrogenation herein) takes place at least in logistics and " ALK " refers to alkylation step.Any step, stage or the unit represented by round rectangle can only comprise key step in practice, or more generally wherein can comprise other one or more step, these steps are chosen wantonly in the present invention, perhaps only are only main in preferred embodiments.This not shown other step comprises for example common various types of distilation steps that adopt in the practice of this area.

In Fig. 9-18, " DIST " of existence is meant a distilation steps, and " SORO/P " of existence is meant adsorbs olefins/paraffinic hydrocarbons separating step, for example is used for after this OLEX of UOP in the stage (C) of the modification one-level OXO alcohol preparation that will describe in detail ^_Method, wherein " OXO " of Cun Zaiing is meant the carbonylation step.This processing step is known in the art: referring to " background technology " part.

After afore mentioned rules had been arranged, we are for example clear a kind of method of Fig. 1 as can be seen, and it has two fractionation by adsorption steps (the fractionation by adsorption stage (a) that after this defines according to the present invention jointly) in order, then is a dehydrogenation step (step after this (b)); Thereafter an optional alkylation step (step (c) after this).Though it is optional that step (c) is broadly said so in the present invention, but it is present in all preferred embodiments that relate to modified alkylbenzene produced according to the present invention, and (d) sulfonation procedure, (e) neutralizing effect are arranged thereafter when the alkyl benzene sulfonate surfactant of preparation modification usually and (f) mixes to be mixed with life cleaning product.Step (d)-(f) adopts various conventional equipments and not shown in Fig. 1-8.

In the method for Fig. 1, hydrocarbon charging 1 is delivered to the fractionation by adsorption step that first adopts 4-5 dust zeolite beds, for example one according to US 2,985,589 step.Linear hydrocarbon stream is discharged as discharging logistics 6.As a comparison, the logistics 6 that comprises the linear hydrocarbon of vast scale in the production of conventional linear alkyl benzene will be transported to DEH and not have step SOR 5/7 and relevant various logistics.In the inventive method, keep intermediate and be rich in ramose hydrocarbon stream 2 and be delivered to second fractionation by adsorption step according to Fig. 1.Second fractionation by adsorption step adopts the porous medium of particular type and produces and enter being rich in ramose logistics 3 (product in Ding Yi stage (a) after this) and discharging logistics 7 of dehydrogenation reactor (DEH).The porous medium of preferred particular type is " wide aperture " zeolite, the aperture that is characterized as the zeolite that its pore size adopted greater than preparation linear alkyl benzene of this zeolite herein, most preferred pore size for greater than about 5 dusts to about 7 dusts (though can adopt bigger porous material), and its pore size can be able to " turning down " by for example adopting tin alkyl.Logistics 4 is represented and is rich in the ramose hydrocarbon after the dehydrogenation, and round-robin branched chain alkane is represented in logistics 8.Also illustrated the alkylation step that is included in the preferred embodiment of the invention according to of the present invention simultaneously.By the ejecta of alkylation step is as the defined modified alkylbenzene of other parts herein.

Fig. 2 is the synoptic diagram of various steps in another embodiment of the inventive method.Though roughly be similar to the method for Fig. 1, the method for Fig. 2 has great difference, specifically in the fractionation by adsorption step pore size on its adsorption bed with above-mentioned opposite.

Fig. 4 is the synoptic diagram of one embodiment of the invention, and it starts from as from conventional linear alkyl benzene production technique or from the hydrocarbon charging 23 of branch's waste liquid of the linear detergent alcohol method of routine.Adopt the fractionation by adsorption step of the specific porous medium of use to obtain discharging logistics 27 and be rich in ramose logistics 24.Latter's dehydrogenation in being denoted as the step of DEH.The porous medium of preferred this particular type be the zeolite of its pore size greater than the used zeolite pore size of preparation linear alkyl benzene, and most preferably its pore size is greater than about 5 dusts about 7 dusts extremely.Hydrocarbon stream after the dehydrogenation 25 is delivered to alkylation step ALK, transfers out modified alkylbenzene product 26 by this step.Optional recycle stream is expressed as 28.

Fig. 3 is that expression one is similar to Fig. 4 but adopts different substantially chargings and the synoptic diagram of one embodiment of the invention that middle process streams is formed.For example, Fig. 3 utilization has the C10-C14 paraffinic hydrocarbons part of fixed linear/branched chain alkane ratio as charging 17, therefrom shift out various ring compounds as the inventive method part, aromatic hydrocarbons, gem-dimethyl-, ethyl-or than ethyl high-grade branch hydrocarbon more.

When being compared, Fig. 3 and Fig. 4 can see that because the profile of step structure is identical, therefore the illustrational method of institute is identical.Difference is owing to the charging that changes hydrocarbon obtains significantly different result.Fig. 4 employing as hydrocarbon charging 23, obtains being mainly ramose modified alkylbenzene 26 from the waste liquid flow in the linear alkyl benzene production unit.The method that the method for Fig. 4 can be used as a kind of " additional (add-on) " is established in the linear alkylbenzene of the standard production plant.On the contrary, Fig. 3 adopt and to derive from kerosene, in linear alkylbenzene production unit in not processed jet (jet)/diesel oil the mixture of the linear and branched chain alkane of institute's inherent as the hydrocarbon charging.The method of Fig. 3 obtains containing the modified alkylbenzene of the mixture of methyl ramose (according to the present invention for unconventional) and linear (routine) alkylbenzene.The method of Fig. 3 can be used as " independent " (stand-alone) equipment set up and need not be connected on the conventional linear alkyl benzene production unit.What these observationss only should not be looked in order to present method to be described better is restricted condition.

Fig. 5, Fig. 6 and the synoptic diagram of Fig. 7 for other embodiment of the present invention of other different hydrocarbon chargings of adjusting.More particularly, these figure illustrate to regulate the whole bag of tricks of blended paraffin/olefin feed.

Fig. 8 shows in greater detail and sees the structure that is set forth in the special fractionation by adsorption among other method synoptic diagram such as Fig. 1 and Fig. 6.Each square frame is represented an adsorption separation unit.Separating being arranged vertically by turning valve (RV) of (AC on each part left side) of bed at each square frame internal adsorption controls.Finish fractionation by adsorption by in post RC and EC, distilling.The Far Left fractionation by adsorption indicates the logistics of " charging ", " extracting solution " and " raffinate " corresponding to the logistics that indicates " 1 ", " 6 " and " 2 " among Fig. 1.The raffinate stream of first fractionation by adsorption (extracting solution that is not had in the conventional linear alkyl benzene condition of production) becomes the charging of second fractionation by adsorption.The raffinate of second fractionation by adsorption is corresponding to the logistics among Fig. 17 among Fig. 8.The extracting solution of second fractionation by adsorption is corresponding to the logistics among Fig. 13 among Fig. 8: this is to obtain dehydrogenation and/or alkylating logistics in the methods of the invention.

As mentioned above, Fig. 8 also illustrates in greater detail the situation of one fractionation by adsorption herein.Therefore, though in Fig. 2,3,4,5 and 7 all not shown situation that is connected, adopt the concrete unitary any single fractionation by adsorption situation that interconnects representative graph 2,3,4,5 in more detail and 7 suitably shown in two square frames of Fig. 8.

In Fig. 1-7, adopt following regulation: be denoted as the expression left on the fractionation by adsorption of " SOR " hydrocarbon part through porous medium absorption, and the part of the sliding absorption of the expression of under the fractionation by adsorption that is denoted as " SOR ", leaving.Sometimes the part of " last " being left is called " adsorbate " or " extracting solution " in the art, and the part of sometimes " down " being left is called " raffinate " or waste liquid.Use the regulation of " last " and " down " to make the reading method synoptic diagram become convenient herein, but the enforcement of the inventive method should be confined in any specific geometrical configuration.

Employing is used for the similarity principle of Fig. 1-8, Fig. 9 has illustrated the method that alkene comes production modification one-level OXO alcohol in the medium chain methyl branch with the carbonatoms that is suitable for the washing composition application as intermediate that adopts, wherein the OXO catalyzer turns to alpha-olefin with a large amount of pre-isomeries of interior alkene, carries out oxo process on the main then carbon atom endways.More specifically, thick hydrocarbon charging 51 employing distillation tower DIST distill and guarantee that the hydrocarbon charging is applicable to the remainder of present method.The paraffinic hydrocarbons that charging 1 can be desirably narrower carbon range cuts branch.Also obtain light cut 52 and heavy cut 53, but can not be further used for preparing OXO alcohol of the present invention.Make the simulation moving-bed adsorption separation system of the SOR 5/7 of hydrocarbon charging 1 by comprising cell S OR4/5 and back, each unit is applicable to the MOLEX_ type, by shown in order connect.Setting structure makes to be rich in linear paraffinic hydrocarbons and to be denoted as 6 the linear logistics (adsorbate) that is rich in Fig. 9 and discharges from cell S OR4/5.Branch's intermediate stream (raffinate) 2 that be rich in that is rich in methyl ramose paraffinic hydrocarbons enters cell S OR 5/7.Dump the discharging current 7 that contains unwanted ring-type, aromatics, ethyl branch and higher branched chain alkane from SOR 5/7.So far the affluent-dividing 3 that is rich in from SOR5/7 is the methyl ramose alkane hydrocarbon stream of purifying, and enters dehydrogenator DEH (for example PACOL_ type), and 20% alkane hydrocarbon stream mainly is converted into corresponding monoene at the most there.The affluent-dividing (alkene stream) 4 that is rich in that contains described monoene and unreacted paraffins and some two olefinic impurities enters SOR O/P, and SOR O/P is a simulation moving-bed adsorption separation system, and design adopts OLEX_ or similarity method to isolate alkene from paraffinic hydrocarbons.For example Shi Yi sorbent material is copper or the silver on X zeolite or the Y.To be rich in affluent-dividing (adsorbate) 55 (so far most be methyl ramose alkene) from the olefinic of the purifying of SOR O/P and send into the OXO reactor.Cycling stream 8 is mainly methyl ramose paraffinic hydrocarbons.Design OXO reactor is used for being called as in the art " a step low pressure OXO method ", and adopting in this method is not the catalytic metal of iron, and described metal adopts bulk phosphine part (referring to the bibliography in the background) modification.Adopt distillation and other householder method (not marking) that thick modification one-level OXO alcohol (product stream 58) is separated and clean the one-level OXO alcohol of modification from material capable of circulation, so far from material capable of circulation, separate and be called stream 57.For the more detailed description of the composition of each stream form referring to the back.

Figure 10 is similar to Fig. 9, and difference is that it adds one or more treatment steps behind dehydrogenation step, and hydrogenation is converted into monoene at two olefinic impurities of dehydrogenator generation and with it.This is a kind of typical DEFINE_ type stage of UOP Corp registration.Also there is one or more other aromatics removal step, the PEP_ method of UOP for example, the aromatic impurities that is mainly used in certain embodiments, form.

Figure 11 is similar to FIG. 10, and difference is that it adopts simplified method: adopt the charging of alkene alkane mixture as the OXO reactor, so far cycling stream 8 is the main part (＞70%) of OXO reactor output.

Figure 12 is similar to FIG. 10, and difference is that cell S OR 4/5 and SOR 5/7 have opposite configuration.

Figure 13 is similar to Figure 11, and difference is that cell S OR 4/5 and SOR 5/7 have opposite configuration.

Figure 14 is similar to Figure 12, and difference is: remove SOR 4/5 and make linear and mixture methyl ramose compound use in entire method.Final product is linear and mixture methyl ramose one-level OXO alcohol.

Figure 15 is similar to Figure 13, and difference is: remove SOR 4/5 and make linear and mixture methyl ramose compound use in entire method.Final product is linear and mixture methyl ramose one-level OXO alcohol.

Figure 16 is similar to FIG. 10, and difference is to dispose described device and makes olefinic be rich in ramose logistics 55 can be used to prepare modified alkylbenzene and/or modification one-level OXO alcohol.

Figure 17 is similar to Figure 11, and difference is to dispose described device makes methyl branch olefin stream 54 can be used to prepare modified alkylbenzene and/or modification one-level OXO alcohol.

Figure 18 is similar to Figure 14, and difference is to dispose described device and makes methyl branch and linear olefin stream 61 can be used to prepare to contain the product of modified alkylbenzene and/or modification one-level OXO alcohol and corresponding linear counterpart.

The present invention's general introduction

In preferred embodiments, the present invention relates to prepare alkylbenzenesulfonatsurfactants surfactants or the pure and mild deutero-thus of modification one-level OXO tensio-active agent, perhaps even prepare the method for these dissimilar surfactant mixtures.The inventive method is from being described in more detail defined hydrocarbon charging in other place of this paper." modification " refers to a kind of very special branch pattern.Particularly, for example in OXO alcohol in full, " modification " is meant and be not the locational methyl of common OXO branch, avoid influencing simultaneously biodegradable branch location or type substantially.Preferably " modification " be meant the medium chain position, single low alkyl group, especially the OXO alcohol that replaces of monomethyl.This method comprises fractionation by adsorption stage and (c) alkylation stage when preparation modified alkylbenzene and/or alkylbenzene sulfonate of (a) concrete definition.Useful especially for detergent manufacturer is that the hydrocarbon charging can be fractionation by adsorption raffinate or the waste liquid that derives from linear alkyl benzene production process or the conventional linear detergent alcohol method, though also can use other charging such as jet/diesel oil or alkene.

When charging is paraffinic hydrocarbons, the embodiment of method of the present invention also comprise usually and preferably (b) dehydrogenation stage of being inserted between fractionation by adsorption and the alkylation order and, when modified alkylbenzene (c) alkylation stage when being required product.Clearly certain embodiments is not must be obligato when charging is alkene.Generally speaking, preferred alkyl carry out after the stage (d) sulfonation, (e) neutralization and (f) by mixing, agglomeration, condense, spraying drying etc. is mixed with the life cleaning supplies.Can there be more than one step in any stage and comprises various options as distillation, and condition is that it comprises specified at least minimum unit.

When the preparation modified alkylbenzene, stage (a) fractionation by adsorption comprises and will be selected from the alkene charging, the hydrocarbon of paraffinic feedstock and the charging of blended olefin/paraff iotan is fed to small part and is separated into and comprises that at least a ramose acyclic hydrocarbous ratio increases for described hydrocarbon charging (as surpassing comparatively speaking at least about 50%, absolute its weight percentage is at least about 10% (weight)) be rich in the ramose logistics, with usually one or more other logistics, as comprise with respect to as described in linear no cycloaliphatic hydrocarbon ratio increases for the hydrocarbon charging (, definitely being at least about 10% (weight)) at least a as surpassing comparatively speaking at least about 50% be rich in linear logistics.Other logistics that is present in this method can change on forming.This class logistics comprises the discharge logistics, wherein from the amount of the ring-type of charging and/or the undesirable component of aromatics usually above its amount in charging, also can have recycle stream etc.

More particularly, the inventive method fractionation by adsorption part (a) has one or more step, comprise the hydrocarbon charging at first is provided, at least one step is selected from the fractionation by adsorption (preferably) that adopts porous medium to carry out then, employing is selected from the clathration that cage combination compound that urea, thiocarbamide and alternative cage close acid amides carries out, and various combination.This stage adopts simulated moving bed adsorption tripping device known in the art (specifically referring to US 2,985,589, entire chapter is incorporated this paper into herein), it comprises that at least one supports the bed of described porous medium or cage combination compound (for example referring to US 2,985,589 Fig. 1 and relevant specification sheets) and in described bed, be used to simulate and the described porous medium of hydrocarbon stream adverse current or the device of cage combination compound motion, be generally the turning valve (specifically referring to US 2,985,589 Fig. 2) of height Specialty Design.

Concrete unusual and novel part is in the inventive method specification sheets, mimic moving-bed fractionation by adsorption bottom line is used for extracting and mainly is rich in the ramose logistics herein, that is to say exactly opposite with the practice that is used for the production of linear alkyl benzene sulfonate surfactant.This main difference is also relevant by different forming (comparing with conventional practice) with bed accessory, that is to say, have at least one to comprise the bed that is different from 4-5 dust zeolite (being generally used for the production of linear alkyl benzene), by having bigger pore size and rebuilding processing units (particularly described bed and described equipment), they carry out different connections with the processing step of being correlated with like this.More particularly, make up these devices, and be rich in linear but can be used for any logistics of other purpose or it is discharged from flow process of the present invention so that make the ramose logistics by whole flow process, perhaps be rich in ramose logistics coexistence.In addition, (or the stage (A) in the stage of the inventive method (a), when preparation modification one-level OXO alcohol) comprise aptly and use at least a tool minimum-value aperture size that is selected from that described pore size is no more than about 20 dusts, more preferably no more than about 10 dusts at least greater than the porous medium of selecting the required pore size of the linear acyclic hydrocarbous of absorption.

Surpass about 10% paraffinic hydrocarbons and constantly have high level according to appointment when 11%-90% or higher paraffinic hydrocarbons when described hydrocarbon charging comprises, preferred the inventive method comprises that another one makes the described step (b) that is rich in the ramose logistics to the small part dehydrogenation.Adopt various known catalyzer and condition can carry out dehydrogenation.

When the preparation modified alkylbenzene, do not consider the type of charging, the inventive method preferably includes (c) in the presence of alkylation catalyst, make by one or two abovementioned steps (optional have a fractionation by adsorption step of dehydrogenation step, condition be rich in the ramose logistics finally comprise usually at least about 5%, more generally at least about 15%, be generally 5%-90% or higher alkene) the prepared ramose logistics that is rich in reacts with the aromatic hydrocarbon that is selected from benzene, toluene and composition thereof.Preferred herein alkylation step have from 0 about 40 to being no more than, preferably be no more than about 20 low internal (position) isomer selectivity, and in the other parts of this paper, describe more fully and define.In the document of modified alkylbenzene production so low alkylation optionally alkylating believe that itself just has novelty.

Preferred methods herein also preferably satisfy at least one, the more preferably requirement below two: first, that (a) device of described stage comprises is a kind of, two or more described equipment and at least two described beds, and at least one described bed comprises that the composition that is different from another described bed holds back the porous medium that the methyl ramose does not have the cycloaliphatic hydrocarbon ability with raising.For example, preferred especially pore size surpasses about 5 dusts to the zeolite that is no more than 7 dusts.The second, when preparation during modified alkylbenzene, described step (c) has from 0 about 40 to being no more than, the preferred internal (position) isomer selectivity of lower (so further definition of back).

Preferred herein the whole bag of tricks is to operate with (collecting linear material so that further process and discharge most of branch material) the opposite and inconsistent mode of putting into practice that routine is used to prepare alkyl benzene sulfonate surfactant.In addition, in order to realize this change, we find to be necessary to use unconventional the interconnecting of the fractionation by adsorption operation that further describes in this manual and illustrate.

In the various herein preferable methods, the described simulated moving bed adsorption tripping device in the described stage (a) comprises two rather than a described equipment simultaneously.In the middle of the branching process of specific type, number of devices that is adopted and structure thereof are quite important in the production of finishing preferred composition of the present invention and raising hydrocarbon stream.

In addition, have in the preferred method of two described beds at some, each comprises some different described porous mediums of forming, each described bed is controlled by a described equipment, have 8 mouths (as US 2 with each described equipment is minimum, define in 985,589) to realize the simulated motion of described porous medium in described bed.The vertical position that also preferred each described bed is divided at least 8 inferior beds distribute (referring to US 2,985, the Fig. 1 in 589).The also preferred stage (a) is all used porous medium rather than cage combination compound in described bed simultaneously.

When the preparation modified alkylbenzene, method herein can have one or more step after alkylation step.These steps can comprise carries out the other step of sulfonated (d) to step (c) product.Can there be pair step (d) product to carry out the other step of neutral (e) after the sulfonation.Can have after these steps and step (d) or product (e) are cleaned product additive material with one or more carry out blended (f), take this to generate cleaning product.

The present invention also comprises by the prepared modified alkylbenzene of any method herein; With by any method herein prepared, with the modified alkylbenzene sulfonic acid or the alkylbenzenesulfonatsurfactants surfactants of forms such as the form of the form of the form of the form of any known salts such as sodium salt, sylvite, ammonium salt, substituted ammonium salt; And by the prepared life cleaning product of any method herein.

Equally, when described modification one-level OXO alcohol prepares anion surfactant from here, the present invention includes the form of the salt of specified tensio-active agent above all.

Cleaning product embodiment (no matter being to add modified alkylbenzene sulfonates and/or add any tensio-active agent that derives from modification one-level OXO alcohol described herein in them) comprises detergent for washing clothes, dish washing detergent, hard surface cleaner etc. herein.In these embodiments, by the content of the prepared modified surface promoting agent of the inventive method is that about 0.0001%-is about 99.9%, to be generally about 1%-about 50%, and described composition comprises also that about 0.1%-is about 99.9%, is generally various cleaning product additive materials such as cosurfactant, washing assistant, enzyme, SYNTHETIC OPTICAL WHITNER, bleach boosters, activator or the catalyzer etc. of about 1%-about 90%.

The present invention also have alternative use paraffinic feedstock (wherein two concrete configurations almost with the identical fractionation by adsorption step of stage (a) that is used to produce modified alkylbenzene described herein, be other step except benzene alkylation step (c), obtain various useful cleansing surfactants thereafter) embodiment.These replace the alkylating step of steps (c) to comprise being selected from least one following step: dehydrogenation, chlorination, sulfoxidation and be oxidized to the pure and mild C8-C20 of the being oxidized to carboxylic acid of C8-C20 or its salt, optional following steps thereafter: glucamideization (glucosamidation) is converted into non-carbohydrate-deutero-acidamide surfactant (as a glycollic amide tensio-active agent or any this acid amides that does not have glucose moiety) and sulfonation (being converted into ester).Other alternate embodiment adopts and comprises 20% or the hydrocarbon charging of more methyl-ramose alkene; Same this method has stage (a) the fractionation by adsorption step of special configuration.Subsequent step can comprise that employing benzene or toluene carry out alkylation step, and optional is thereafter sulfonation procedure; Adopting phenol to carry out alkylation step, is thereafter at least one step in alkoxylate, sulphating, sulfonation procedure or its various combinations; Carbonylation becomes alcohol, and optional is thereafter at least one following steps: alkoxylate, glycosylation, sulphating, phosphatization step or its various combinations; Sulfonation; Epoxidation; Bromine hydrogenation is thereafter the amination step and be oxidized to amine oxide; And phosphorylation.

The present invention also comprises by the prepared various tensio-active agents of these methods with by the prepared various cleaning product of these methods.The present invention also comprises various useful especially embodiments, and wherein the fractionation by adsorption in stage (a) comprises the separating step that at least one adopts organo-metallic grafted mordenite such as tin grafted mordenite.The present invention comprises that also use grafting mordenite is used for producing the tensio-active agent of detergent surfactant and any correspondence and the method for life products (being prepared from by using these special porous mediums at any aforesaid method).

The present invention has many other important embodiment and branches.Therefore the present invention includes and contain following method: (A) to stage of small part separate hydrocarbons charging, described hydrocarbon charging comprises the ramose aliphatic hydrocrbon, more specifically for having about 8 paraffinic hydrocarbonss to about 20 carbon atoms, make being rich in the ramose logistics and choosing any one kind of them or multiple of its branch's acyclic hydrocarbous that is separated at least one increase ratio that contains described relatively hydrocarbon charging:

-contain described relatively hydrocarbon charging the increase ratio linear aliphatic hydrocrbon be rich in linear logistics; With

-contain the discharging current of ring-type and/or aromatics and/or ethyl or more senior branched-chain hydrocarbon; The wherein said stage, (A) comprising:

-described hydrocarbon charging is provided; With

-adopt the described charging of porous medium fractionation by adsorption to become described stream;

The described stage (A) is adopted simulation moving-bed adsorption separation device, and this equipment comprises following two kinds:

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

The equipment of-simulation and the motion of the porous medium of hydrocarbon stream adverse current in described bed; Be another stage (B), (C) and (D) (any in them has one or more steps) subsequently:

(B) (ⅰ) make the stage (A) be rich in affluent-dividing to small part dehydrogenation form thus contain monoene be rich in branch's olefin stream (optional vast scale, up to 80% or higher paraffinic hydrocarbons can exist with impurity such as diene and/or aromatic impurities), optionally handle the described branch's olefin stream that is rich in to reduce the wherein content of aromatic impurities for one or more (ⅱ) handles the described branch's olefin stream that is rich in the content that reduces diene impurity wherein with (ⅲ) subsequently; (C) optional known sorbent material or the porous medium of adopting passes through adsorption separating method, at least the described described monoene that is rich in branch's olefin stream in partial concentration stage (B), condition is the porous medium that described sorbent material or porous medium are different from stage (A), and be suitable for olefin/paraff iotan and separate (as X zeolite or the Y that copper is handled or silver is handled), and optional endless chain alkane simultaneously is to described dehydrogenation stage (B); And

(D) in the presence of the OXO catalyzer, make generate in the stage (B) or choose further spissated described be rich in branch's olefin stream and carbon monoxide and H-H reaction in the stage (C) wantonly, form the one-level OXO alcohol of modification thus.

In the description of method, term " stage " is meant the concentrated combination that can regard identical one or more processing steps as herein.For example (A) is a fractionation by adsorption stage, is the improved MOLEX_ stage by UOP Corp. registration basically, disposes in order to improve branch's content of (but not as under normal circumstances reducing) hydrocarbon at this unconventionally.Can choose wantonly the additional step that comprises as the part of same phase as distillation, add use simultaneously than lower boiling hydrocarbons clean sorbent material or remove step etc. (being known in the art).(B) be dehydrogenation stage, comprise dehydrogenation step at least but generally include as above those steps of describing of mask body of other optional step.The basic technology technology that is used for (B) can be UOP Corp. registration as the PACOL_ method.(C) be conventional OLEX_ stage (also providing) basically by UOP Corp..(D) being preferably this class is called " a step low pressure OXO " in the art and also is the OXO stage known in the art.As other step of this method, the stage, (D) can replenish other optional step, for example catalyst removal etc.Except as otherwise noted, otherwise when stage of the embodiment that is meant the inventive method, agreement adopts capitalization (A, B, C herein ...), wherein said method comprises preparation modification one-level OXO alcohol.

Derive and the tensio-active agent that comes has obvious advantage by these new pure and mild alkylbenzenes noted earlier of modification one-level OXO, as easier dissolving under the condition of given chain length/carbon number (is important from the cold washing of increased popularity); Have during with the adding detergent particles and exceed unexpected high dissolution rate.Therefore the pure and mild alkylbenzene of OXO itself also is used to prepare cleaning compositions as heavily using as a servant detergent for washing clothes, tableware washing lotion etc.Except as otherwise noted, otherwise herein all percentage ratios, ratio and ratio are all calculated by weight.Except as otherwise noted, otherwise all temperature be degree centigrade (℃).The relevant portion of all citation documents is incorporated this paper by reference into.

The present invention describes in detail

In one embodiment, the present invention relates to a kind of method that is used for preparing alkylbenzenesulfonatsurfactants surfactants from the hydrocarbon charging.Use term " charging " and/or " raw material " of same meaning to represent any hydrocarbon that can be used as raw material in the inventive method herein.On the contrary, term " logistics " is commonly used to represent to experience the hydrocarbon of at least one processing step.Generally speaking, hydrocarbon charging herein contains the no cycloaliphatic hydrocarbon (no matter be alkene or paraffinic hydrocarbons, maybe can comprise the mixture of these alkene and paraffinic hydrocarbons) of useful ratio.This raw material also generally includes the ring-type and/or the aromatic hydrocarbon impurity (as seen in kerosene, jet/diesel oil (middle cut) hydrocarbon cut) of various different quantitiess.Alkene and paraffinic hydrocarbons usually simultaneously exist with branch and linear form in raw material.In addition, generally speaking, the branch's form in the raw material can meet or not meet requirement of the present invention.The purpose that the invention provides cleaning product significantly is different from for example gasoline production (wherein for the highly poly-methyl branch of boosting of octane rating needs hydrocarbon).The invention provides the whole bag of tricks that is used to separate the hydrocarbon charging that needs form especially that is used for cleaning product, and with its various useful tensio-active agent intermediate that is mixed into tensio-active agent (especially some modified alkylbenzene sulfonates and/or based on the tensio-active agent of modification one-level OXO alcohol) and cleaning product and is used for this product.

The term " modification " of uniting use with the spawn of the inventive method refers to product and contains the branch of unusual specific type and depart from linear structure (this structure is now usually by preferred and be used for the cleaning product tensio-active agent) astoundingly.Term " modification " also is used for herein product and conventional high ramose cleansing surfactants structure (for example those that find in the tetrapropylene benzene iodate) difference are come, and other conventional branched structure comes as " (two-tailed) of two tails " or " Guerbet " or the difference of 3-acetaldol deutero-branched structure with all.

In general hydrocarbon charging herein can be varied, but generally includes various methyl-branches such as monomethyl, dimethyl (comprising gem-dimethyl), trimethylammonium, many methyl, ethyl and senior alkyl branch.The hydrocarbon charging can contain quaternary carbon atom.Yet when after this present method comprised the alkylation step described, the patience of quaternary carbon atom was too strong in the charging.Have the OXO operation stage and do not having in embodiment of the present invention of alkylation stage, preferred charging does not herein have quaternary carbon atom substantially.The required various components that are used for the object of the invention comprise monomethyl-branch, dimethyl-branch (except gem-dimethyl-branch) and the trimethylammonium-branch of (especially when carbonatoms surpass about 14 time) part to a certain extent.The hydrocarbon charging also comprises various useful ratios such as 5%-40% or higher acyclic hydrocarbous (have about 20 carbon atoms of about 9-usually, depend on the cleaning product tensio-active agent or the required type of cleaning product that adopt the preparation of gained modified surface promoting agent).More preferably the no cycloaliphatic hydrocarbon of raw material comprises about 16, about 14 carbon atoms of 11-more preferably from about of about 10-when the alkylbenzene sulfonate of preparation alkylbenzene of modification and modification.

The inventive method comprises a specific fractionation by adsorption stage, and in addition, for the alkylbenzene and the alkylbenzene sulfonate that prepare modification, alkylation stage also is absolutely necessary.When raw material is paraffinic hydrocarbons, the embodiment of the inventive method also comprises the dehydrogenation stage that interts between fractionation by adsorption and alkylation order usually and preferably, perhaps is being called when the one-level OXO for preparing modification is pure between the fractionation by adsorption type and OXO operation stage of SOR 4/5 among the figure or SOR 5/7.Generally speaking, alkylation or OXO can have other various steps such as sulfonation after the stage, usually thereafter for neutralization and by mixing, agglomeration, condense, spraying drying etc. is mixed with life cleaning product with it.In general any stage can have more than one step simultaneously, and condition is the step which comprises at least a minimum.

Stage (a) is that fractionation by adsorption comprises and will be selected from the alkene charging, the hydrocarbon of paraffinic feedstock and the charging of blended olefin/paraff iotan be fed to small part be separated into comprise at least a for described hydrocarbon charging ramose acyclic hydrocarbous (especially above-mentioned required all kinds, particularly methyl-ramose paraffinic hydrocarbons or methyl ramose one alkene) (surpassing at least about 50% of increasing of ratio as relative charging, more preferably surpass about 100% at least, normally three times, four times or higher, absolute its weight percentage is at least about 10% (weight), be generally at least 20%, 30%-about 90% or higher more preferably) be rich in the ramose logistics, with optional following one or more materials: comprise that for described hydrocarbon charging linear no cycloaliphatic hydrocarbon ratio increases (as surpassing comparatively speaking at least about 50%, more preferably surpass about 100% at least, normally three times, four times or higher, definitely be at least about 10% (weight), be generally at least 20%, 30%-about 90% or higher more preferably) be rich in linear logistics; With the discharge logistics that comprises ring-type and/or aromatic hydrocarbon or other various impurity such as gem-dimethyl hydrocarbon, ethyl-ramose hydrocarbon or senior-ramose hydrocarbon.

Other various logistics that are present in the inventive method can change on forming to some extent.These logistics comprise the discharge logistics, wherein surpass its amount in charging usually from the ring-type of charging and/or the amount of the undesirable various components of aromatics; Recycle stream with various compositions of various piece according to method of attachment etc.Can adopt various known methods herein, as US 5,012,021 or the method for US 4,520,214 (both all incorporate this paper by reference into), adopt catalysts selective that various impurity (as some diolefins) are converted into an alkenes.Other the whole bag of tricks that herein can choose wantonly in conjunction with the aromatic byproducts that generates in the paraffin dehydrogenation process with selective removal comprises US 5,300,715 and US 5,276, those methods of 231, comprise the various extrectants that uses one or more aromatics removal zones (removal zones) and/or be used for aromatic hydrocarbon, as tetramethylene sulfone and/or quadrol.

In more detail, the inventive method be used for improve fractionation by adsorption stage of branch's hydrocarbon content of charging or part and have one or more and comprise that at least one is selected from step that suitable hydrocarbon charging is provided and at least one and is selected from the fractionation by adsorption step that adopts porous medium to carry out, adopts the cage combination compound that is selected from urea, thiocarbamide and alternative cage to close the step that cage that acid amides carries out closes step and various combinations thereof.More preferably when adopting various combination, at least one step is the fractionation by adsorption step of (after this will do more detailed description) porous medium of employing wide aperture type.(or the stage (A) in stage (a), when being used to prepare modification one-level OXO alcohol) adopting can be from simulated moving bed adsorption tripping device known in the art (specifically referring to US 2,985,589, entire chapter is incorporated this paper into herein), it comprises that at least one carries the bed of described porous medium or cage combination compound (for example referring to US 2,985,589 Fig. 1 and relevant specification sheets) and in described bed, be used to simulate device with the described porous medium of hydrocarbon stream adverse current or the motion of cage combination compound (specifically referring to US 2,985,589 Fig. 2 and relevant specification sheets, or the industrial now various variants that are used to produce linear alkylbenzene sulfonate).Mentioned equipment is generally the turning valve of height Specialty Design.Generally speaking, the type of this valve of available is identical with the current type that is used for linear alkyl benzene herein.Can adopt used in the art various absorption separation conditions such as pressure, temperature and time.For example referring to US 2,985,589.

The concrete unusual and novel part of the inventive method is that mimic moving-bed fractionation by adsorption step bottom line is used for extracting and mainly is rich in the ramose logistics herein, that is to say exactly opposite with the practice that is used for the production of linear alkyl benzene sulfonate surfactant.This main difference also with change bed and form so that make it contain the porous medium that is different from the 4-5 dust zeolite that is used in the production of linear alkyl benzene usually and rebuild processing unit (particularly described bed and described equipment) so that make it be connected relevant with the processing step of being correlated with.More particularly, make up these devices, and be rich in linear but can be used for any logistics of other purpose or it is discharged from flow process of the present invention so that make the ramose logistics by whole flow process, perhaps be rich in ramose logistics coexistence.

When described hydrocarbon charging comprises when being less than about 5% alkene, the inventive method preferably includes the another one step (b) of the product generation part dehydrogenation that makes the stage (a) at least, perhaps step (B) (when the one-level OXO of preparation modification alcohol).Adopt any known dehydrogenation catalyst can carry out dehydrogenation, and after this described further again as De-H series from UOP.Various dehydrogenation reaction conditions are similar to those conditions that adopted in the linear alkyl benzene sulfonate production now.

When preparing the alkylbenzene of modification, no matter what type handled raw material is, the inventive method preferably includes the product that makes stage (a) (or when stage (b) when also being present in above-mentioned steps, the stage (a) and the product of (b) thereafter) and reacts in the presence of alkylation catalyst with the aromatic hydrocarbon that is selected from benzene, toluene and composition thereof.As do in the other parts herein describe more fully and define, preferred herein alkylation step has from 0 to about 40, preferably be no more than about 20, the low internal (position) isomer selectivity more preferably no more than about 10.So low internal (position) isomer selectivity believes that itself just has novelty.

In a pattern, alkylation step herein carries out in the presence of excessive paraffinic hydrocarbons, then paraffinic hydrocarbons is reclaimed and is circulated in the dehydrogenator.In another pattern, alkylation step carries out in the presence of excessive 5 times to 10 times aromatic hydrocarbons.Also can be the various combinations of these patterns.

Note when the final ramose logistics that is rich in be that the product in stage (a) is when having suitable olefin(e) centent (as total alkene above about 5%), this logistics can directly enter into alkylation step (c), then can with the alkane circulation that reclaims to dehydrogenation reactor so that it is converted into alkene to small part.For example referring to Fig. 5,6,7.

Considerablely for the present invention be, preferred methods herein also preferably satisfies at least one, more preferably requires below two: first, that described stage (a) device (perhaps stage (A) device when the one-level OXO of preparation modification alcohol) comprises is a kind of, two or more described equipment (as above-mentioned turning valve or any device that is equal to) and bed as described at least two, and at least one described comprises that being different from another composition of described holds back the porous medium that methyl-ramose does not have the cycloaliphatic hydrocarbon ability with raising.For example, pore size surpasses the pore size be used for the production of conventional linear alkyl benzene and at least up to about 20 dusts, more preferably up to about 10 dusts, also more preferably also suit herein up to the zeolite of about 7 dusts or the material of other porous medium such as some silicon aluminium phosphate or MobilMCM-type, condition be its pore size scope as mentioned above.When the use pore size surpasses the porous medium of about 7 dusts, very need the opening (as passing through) in " turning down " aperture usually at aperture openings place grafting tin alkyl.Incorporate the EP 559 of this paper, 510A into referring to entire chapter.The second, when the alkylbenzene of preparation modification, described step (c) has from 0 about 40 to being no more than, the preferred internal (position) isomer selectivity of lower (as mentioned above and do after this further detailed definition).

In another preferred method, at least one described bed comprises that routine is used to produce the porous medium of linear alkylbenzene; Described bed is connected in the described process in the following manner: increasing methyl-ramose to small part does not have cycloaliphatic hydrocarbon and enters ratio in the step (c) in described process, and reduce linear no cycloaliphatic hydrocarbon to small part and enter ratio in the step (c) in described process, described linear no cycloaliphatic hydrocarbon is discharged as discharging flow liquid in the stage (a) at least.In other words, preferred methods herein is to operate with (discharge branch's material and also collect linear material so that further process) the opposite and inconsistent mode of putting into practice that routine is used to prepare alkyl benzene sulfonate surfactant.In addition, in order to realize this change, we find to be necessary to use and have sketched and as unconventional the interconnecting of the fractionation by adsorption operation that further illustrates among herein each figure.

Considerablely be equally in the preferable methods herein, described in (perhaps stage (A) in stage (a), when one-level OXO when alcohol of preparation modification) in the simulated moving bed adsorption tripping device comprise two rather than a described equipment, perhaps one can the described porous medium motion of simulation at least two independent beds single equipment.In other words, for all preferable methods herein, adopt single equipment (being set forth in US 2,985 as seeing, the equipment in 589) not meet the demands.The quantity of equipment and structure thereof are considerably important for the production of finishing preferred composition of the present invention.Therefore, in the hypothesis of this area the unknown, the further purification of linear hydrocarbon can be finished by two equipment and two beds of being connected in series.Highly linear adsorbate of fs can enter into the adsorption separation process in second stage further to purify.Consider its incorrect connection of each stage and cause the linearity of hydrocarbon and purity to increase, therefore this structure is not within the scope of the present invention.Such as already mentioned, the inventive method comprises makes branch's logistics by various steps or stage, requires to be connected with each equipment of congruence.Increased herein ramose specific type in the hydrocarbon stream like this.

Also considerablely in the preferable methods herein be, two described beds are arranged, one comprises the different described porous mediums of forming, each described bed is controlled by a described equipment, and each described equipment is minimum has 8 mouths to realize the motion of the described porous medium of simulation in described bed.The vertical position that each described bed also preferably is divided at least eight inferior beds distributes.The also preferred stage (a) is used porous medium fully in described bed simultaneously.Therefore, the present invention can use and see and be set forth in US 2,985, the conventional bed and the equipment of general type in 589, but its quantity and and process of the present invention between to be connected in the alkylbenzene sulfonate production unit be novel and beyond example.

Simultaneously, for the content of having described in some embodiment that preferred method herein is described better, describedly be rich in linear logistics and be present in the stage (a), and the stage (a) comprising: (a-ⅰ) is describedly to be rich in linear logistics and to be rich in the ramose intermediate stream by a described simulation moving-bed device with described hydrocarbon charging fractionation by adsorption, and discharges the described linear logistics that is rich in by the purpose requirement of described method; Then (a-ⅱ) is described simulation moving-bed by another, will describedly be rich in ramose intermediate stream fractionation by adsorption and be to comprise with respect to described be rich in no cycloaliphatic hydrocarbon branch (particularly methyl-branch) ratio increase for the linear logistics described and be rich in the ramose logistics and comprise with respect to described and be rich in the discharge logistics that ring-type for branch's logistics and/or aromatic hydrocarbon ratio increase at least.

Described discharge logistics in the described step (a-ⅱ) can also comprise and is selected from gem-dimethyl branch hydrocarbon, ethyl ramose hydrocarbon and than ethyl undesirable branch hydrocarbon of high-grade branch hydrocarbon more; And wherein said no cycloaliphatic hydrocarbon that is rich in the ramose intermediate stream and the described described gem-dimethyl branch hydrocarbon that is rich in that branch's logistics comprises that ratio reduces for described hydrocarbon charging, ethyl ramose hydrocarbon and than ethyl high-grade branch hydrocarbon more.Be rich in the patience of this different components in the ramose logistics according to the centre, ethyl ramose hydrocarbon is more acceptable more than gem-dimethyl, ring-type and aromatic component.Generally speaking, " the ratio increase " of any component minimum level in any herein step, " ratio reduction " or " being rich in " are corresponding to any increase (enrichment) of the ratio that can be actually used in the target of having mentioned before the present invention or reduce.This tittle will elaborate in whole specification sheets.

Simultaneously in described method, can obtain described each logistics composition as described porous medium: in described step (a-ⅰ), be selected from the composition of 4-5 dust pore size zeolite and in described step (a-ⅱ), be selected from pore size at least greater than the composition of the porous medium of about maximum aperture size of described step (a-ⅰ) zeolite by selecting following material.

In a further preferred embodiment, stage, (a) comprising: (a-ⅰ) is to comprise linear-and being rich in no cycloaliphatic hydrocarbon logistics and comprising for described hydrocarbon charging ring-type and/or the aromatic hydrocarbon ratio increases at least that first discharges logistics of the no cycloaliphatic hydrocarbon of branch's (for example aforesaid required type) with described hydrocarbon charging fractionation by adsorption, and then (a-ⅱ) is describedly to be rich in the ramose logistics and describedly to be rich in linear logistics with the described logistics fractionation by adsorption that is rich in no cycloaliphatic hydrocarbon; Wherein said fractionation by adsorption adopts described simulated moving bed adsorption tripping device to carry out.Herein except as otherwise noted, otherwise " being rich in the ramose logistics " refers to the final logistics of stage or step (a); Other each qualifier as " intermediary " with predetermined fixed in the expression this logistics title in, though branch's hydrocarbon obtains enrichment, before the fractionation by adsorption stage from present method enters into another stage, still need to be further processed.What also will mention simultaneously is, the stage (a) is can freely comprise other conventional optional step the fractionation by adsorption stage as distillation, and condition is to carry out fractionation by adsorption.Therefore, present industrial MOLEX ^_Equipment also comprises distillation usually and can be used for herein in this stage.

The present invention also comprises a method, discharges logistics and also comprises and undesirablely be selected from gem-dimethyl branch hydrocarbon, ethyl-branch's hydrocarbon and than ethyl branch's hydrocarbon of high-grade branch hydrocarbon more for first kind described in the wherein said step (a-ⅰ); With the wherein said logistics that is rich in no cycloaliphatic hydrocarbon and describedly be rich in each described gem-dimethyl branch hydrocarbon that comprises all that ratio reduces for described hydrocarbon charging of ramose logistics, ethyl-branch's hydrocarbon and than ethyl high-grade branch hydrocarbon more.In these embodiments, by selecting following material can obtain described each logistics composition: in described step (a-ⅱ), be selected from the composition of 4-5 dust pore size zeolite and in described step (a-ⅰ), be selected from pore size at least greater than the composition of the porous medium of about maximum aperture size (maximum is about 10 dusts) of described step (a-ⅱ) zeolite as described porous medium.

More generally, the present invention relates to a kind of method, wherein the stage (a) comprises at least a its minimum-value aperture size that is selected from of use greater than the porous medium of selecting the required pore size of the linear acyclic hydrocarbous of absorption, and described pore size is no more than about 20 dusts.

As mentioned above, preferred herein the whole bag of tricks comprises that the internal (position) isomer selectivity of wherein said alkylation step (c) is 0-20; A preferred alkylation step (c) adopts with corresponding to alkylation catalyst of described internal (position) isomer selectivity and wherein said alkylation catalyst and is selected from simultaneously: to small part tart mordenite with to small part tart beta-zeolite.Preferred alkylation catalyst comprises H-mordenite and H-β mordenite, more preferably to the H-mordenite of small part dealuminzation.

Aspect the alkylbenzene sulfonate of alkylbenzene for preparing modification and modification, the present invention also preferably includes such method, and wherein said hydrocarbon charging comprises that at least about 10% methyl-ramose paraffinic hydrocarbons its molecular weight is at least about 128, is no more than about 282; Described method has described dehydrogenation step (b).More preferably in this embodiment, described hydrocarbon charging comprises that at least about 20% methyl-ramose paraffinic hydrocarbons its molecular weight is at least about 128, is no more than about 226; Described method has described dehydrogenation step (b) and alkylation step (c); The present invention also preferably includes such method, and wherein said hydrocarbon charging comprises that at least about 10% methyl-ramose alkene its molecular weight is at least about 126, is no more than about 280.More preferably in this embodiment, the hydrocarbon charging comprises that at least about 50% methyl-ramose alkene its molecular weight is at least about 126, is no more than about 224; Described method does not have dehydrogenation step (b).

For the correlation method of the one-level OXO alcohol for preparing modification, can expand above-mentioned scope to a certain extent, keeping total carbonatoms is about C ₂₀Or it is higher.More preferably, it is about 254 that 226 the paraffin molecules amount of being limited on above mentioned increases to, and 224 the olefin hydrocarbon molecules amount of being limited on above mentioned increases to about 252.

The most usefully, hydrocarbon charging herein or raw material can be from fractionation by adsorption raffinate or waste liquid in the linear alkyl benzene production process for detergent manufacturer.

Method herein can have one or more step after alkylation step.These steps can comprise another step of (d) sulfonation procedure (c) product.Another step that (e) neutralization procedure (d) product can be arranged after the sulfonation procedure.Can there be (f) to make step (d) or product (e) and one or more cleaning product additive materials carry out the blended step after these steps; Take this to produce cleaning product.

Therefore method herein comprises the highly preferred embodiment with following all other steps: (d) the modified alkylbenzene product of sulfonation procedure (c); (e) the modified alkylbenzene sulfonic acid product of neutralization procedure (d); (f) the alkyl benzene sulfonate surfactant product of step (d) or modified alkylbenzene sulfonic acid (e) or modification is mixed with one or more cleaning product additive materials, take this to form cleaning product.In such embodiment, the modified alkylbenzene with described step (c) product before carrying out described sulfonation procedure carries out fusion with the linear alkyl benzene for preparing by ordinary method.In another such embodiment, in any step after described sulfonation procedure, the modified alkylbenzene sulfonates of described step (d) product and the linear alkyl benzene sulfonate for preparing by ordinary method are carried out fusion.In the embodiment of these fusion, the modified alkylbenzene of preferred method is about 1 with the ratio of linear alkyl benzene: about 100: 1 of 100-.When the more linear product of needs, preferred ratio is about 10: about 50: 50 of 90-.When the more subsidiary product of needs, preferred ratio is about 90: about 51: 49 of 10-.

The present invention also comprises by the prepared modified alkylbenzene of the whole bag of tricks herein; With by the modified alkylbenzene sulfonic acid prepared, that exist with the forms such as ammonium salt of any known salt form such as sodium salt, sylvite, ammonium salt, replacement of the whole bag of tricks herein or the alkyl benzene sulfonate surfactant of modification; And by the prepared life cleaning product of the whole bag of tricks herein.

Cleaning product embodiment herein comprises detergent for washing clothes, dish washing detergent, hard surface cleaner etc.In these embodiments, by the prepared modified alkylbenzene sulfonates of the inventive method, or the OXO of modification one-level from here alcohol etc. derives and the content of the tensio-active agent that comes is about 99.9% for about 0.0001%-, to be generally about 1%-about 50%, and composition comprises also that about 0.1%-is about 99.9%, is generally various cleaning product additive materials such as cosurfactant, washing assistant, enzyme, SYNTHETIC OPTICAL WHITNER, bleach boosters, activator or the catalyzer etc. of about 1%-about 50%.

Be fit to comprise the tensio-active agent of described modification of about 1%-about 50% and the cleaning product additive material of about 0.0001%-about 99% by the preferred life cleaning product of these methods preparation, it is selected from enzyme, nonphosphate, washing assistant, polymkeric substance, activated bleaching agent, catalytically bleaching agent, optical white and composition thereof.The alternative methods embodiment

The present invention has various alternate embodiments, wherein obtains other various steps of useful cleansing surfactants after the fractionation by adsorption step of two special configurations.Therefore, comprise a method herein, it comprises: (I) is separated into the hydrocarbon charging and comprises that (more preferably mainly comprising) is at least about the logistics that be rich in branch hydrocarbon of 85% carbon content for the saturated no cycloaliphatic hydrocarbon of the about C20 of about C8-, the described logistics that is rich in branch's hydrocarbon comprises at least about 10% having methyl ramose paraffinic hydrocarbons, described methyl branch is distributed in the described paraffinic hydrocarbons, makes paraffin molecules have from 0 to being no more than content that about 3 described methyl branch and described branch be positioned at described paraffinic hydrocarbons and makes at least about 90% described branch and occupy position except being formed into gem-dimethyl and/or quaternary groups; Wherein said separation is by comprising that at least two are adopted the simulated moving bed adsorption tripping devices to carry out with the mode of the fractionation by adsorption step of at least two kinds of porous mediums with different pore sizes; (II) is converted into tensio-active agent by other step that at least one is selected from following steps with the described logistics that is rich in branch's hydrocarbon: dehydrogenation, chlorination, sulfoxidation, be oxidized to the pure and mild C8-C20 of the being oxidized to carboxylic acid of C8-C20 or its salt, optional also have a step thereafter, and it is selected from: glucamideization (being converted into non-carbohydrate deutero-acidamide surfactant) and sulfonation (being converted into ester).

In addition, as alternate embodiment, also comprise a method herein, it comprises: (I) is separated into the hydrocarbon charging and comprises that (preferablying mainly comprise) carbon content do not have the logistics that is rich in alkene branch hydrocarbon of the mixture of the mixture of cycloaliphatic hydrocarbon or homologue saturated with it for the alkene of about C8-C20, the described logistics that is rich in branch's hydrocarbon comprises that sum is at least about 10% described alkene and have the saturated homologue of methyl ramose, described methyl branch is distributed in and makes any described no cycloaliphatic hydrocarbon molecule have from 0 to being no more than about 3 described methyl branch and described branch in the described mixture to make at least about 90% described branch at the intramolecular content of described no cycloaliphatic hydrocarbon and occupy position except forming the gem-dimethyl group; Wherein said separation is by comprising that at least two are adopted the simulated moving bed adsorption tripping devices to carry out with the mode of the fractionation by adsorption step of at least two kinds of porous mediums with different pore sizes; (II) is converted into tensio-active agent by other step that at least one is selected from following steps with the logistics that described olefinic is rich in branch's hydrocarbon: adopt benzene or toluene to carry out alkylation step, optional is thereafter sulfonation procedure; Adopting phenol to carry out alkylation step, is thereafter at least one step in alkoxylate, sulphating, sulfonation procedure or its various combinations; Carbonylation, optional be thereafter at least one following steps: alkoxylate, and alkoxylate, glycosylation, sulphating, phosphatization step or its various combinations of oxide compound; Sulfonation; Epoxidation; Bromine hydrogenation is thereafter amination and be oxidized to amine oxide; And phosphorylation.

Because included various alternative approach, the present invention also comprises by the prepared various tensio-active agents of these methods and by the prepared various cleaning product of these methods.

Now discuss and illustrate all respects of the present invention in more detail.The alkylbenzene of modification and alkyl benzene sulphonate (ABS) product salt

As mentioned in general introduction, the present invention includes the method that is used to prepare the alkylbenzenesulfonatsurfactants surfactants that is applicable to various cleaning product such as detergent for washing clothes, hard surface cleaner, dish washing detergent etc.

Term " alkylbenzenesulfonatsurfactants surfactants " and " modified alkylbenzene " refer to the product of the whole bag of tricks herein.The product that the term " modification " that is used for new alkyl benzene sulfonate surfactant or new alkylbenzene (MAB) is used to refer to the inventive method is different from all at the used alkyl benzene sulfonate surfactant of commerce life cleaning compositions on forming.More particularly, the present composition is different from the alkylbenzene sulfonate of so-called " ABS " or biodegradable performance difference on forming, and is different from so-called " LAS " or linear alkyl benzene sulfonate surfactant.At present conventional various LAS tensio-active agents get by several commercial runs, and described method comprises those methods of the alkylating that depends on the catalytic or aluminum chloride-catalytic benzene of HF-.Other various industrial LAS tensio-active agents comprise and pass through DETAL ^_The LAS of method preparation.Adopting the preferred alkyl benzene sulfonate surfactant of preferably low-internal (position) isomer selective alkylation step preparation also to be different from those herein herein on forming fluoridizes zeolitic catalyst system (believe also comprise fluoridize mordenite) by employing linear alkene is carried out the prepared tensio-active agent of alkylating.Be not entangled in theory, we believe that alkylbenzenesulfonatsurfactants surfactants is unique ramose a little herein.They contain a large amount of isomer and/or homologue usually.This a large amount of kind (being generally tens of or even a large amount of) is followed the 2-phenyl isomer of higher total content usually, and the content of 2-phenyl isomer is at least 25%, is generally 50% or even 70% or higher.In addition, modified alkylbenzene sulfonates product herein is different from known various alkyl benzene sulfonate surfactant on various physicalies, as have improved tensio-active agent efficient and the less generation internal (position) isomer that from solution, is separated out, especially in having the situation of the water hardness.Charging of the inventive method and logistics

Term " charging " is used to refer to the material of not processing by the inventive method as yet herein.Yet also can use the term of this charging when a kind of material an optional step in the inventive method (as carrying out fractionation by adsorption on the 5 dust Ca-zeolites) is administered to, condition is that this processing is implemented before first key step of the inventive method is carried out in advance.

Term " logistics " is used to refer to the material of at least one step of almanac inventive method herein.

Unless more specific description is arranged, refers to any hydrocarbon part that contains following more a spot of material at least through processing otherwise term herein " is rich in the ramose logistics ":

(ⅰ) comparatively speaking, compare, increase at least about 10%, preferably at least 100% (promptly two times), more preferably three times, four times or the higher about C20 hydrocarbon of the acyclic C8-of branch with not finished in the methods of the invention parent fraction or charging as yet; Or

(ⅱ) absolute, when the alkylbenzene sulfonate of the alkylbenzene of described method production modification or modification, at least about 5%, be preferably 10% or the hydrocarbon of the higher about C20 of the acyclic C8-of branch, the more preferably from about hydrocarbon of the about C14 of C10-.

Mentioned branch's hydrocarbon can be alkene, paraffinic hydrocarbons or with the olefin/paraff iotan (unless more specific description is arranged) of any mixed.(some preferable methods relates to the one-level OXO alcohol for preparing modification, as shown in Figure 9 with by the higher starting point with paraffinic feedstock, more generally can adopt the alkene charging for the variant of the whole bag of tricks).Branch is preferably monomethyl branch or isolating (non-together with) dimethyl branch.

Unless more specific description is arranged, otherwise " being rich in linear logistics ", term herein refers to hydrocarbon part after any processing, compared with parent fraction of not processing in the methods of the invention or charging, it contains just (n-) acyclic hydrocarbous of higher weight per-cent.

More particularly, the logistics that " is rich in linear " refers to contain at least following any hydrocarbon part through processing than small amount of matter:

(ⅲ) comparatively speaking, compare, increase at least about 10%, preferably at least 100% (promptly two times), more preferably three times, four times or the higher about C20 hydrocarbon of linear acyclic C8-with not finished in the methods of the invention parent fraction or charging as yet; Or

(ⅳ) absolute, at least about 5%, be preferably 10% or the higher about C20 hydrocarbon of linear acyclic C8-.

Mentioned linear hydrocarbon can be alkene, paraffinic hydrocarbons or with the olefin/paraff iotan (unless more specific description is arranged) of any mixed.

Various qualifiers as " intermediary " when being rich in ramose logistics fractionation by adsorption stage (a) by the inventive method fully not as yet with being rich in to be used to refer to when the ramose logistics is used to be called as.Other qualifier can be used to refer to that as " olefinic " or " paraffinic hydrocarbons " etc. alkene that logistics the contains paraffinic hydrocarbons of preponderating still preponderates.

The inventive method (according to comprise alkylating embodiment and according to comprising OXO reaction (or adopting both simultaneously)) in various chargings and logistics further be shown in the following table.Numeral on Far Left one hurdle refers to charging and the logistics in Fig. 1-Figure 18.

Logistics	Logistics Types/title	Exemplary source (charging) or composition (logistics)	Main ingredient
				1	The hydrocarbon charging	Jet/kerosene part, preferably from light crude oil, for the embodiment of preparation modification one-level OXO alcohol, preferred feedstock be narrower cut (as 3,2,1 or carbon extension (spread) or non-integral narrow cut)	B-paraffinic hydrocarbons/l-paraffinic hydrocarbons
2	Be rich in ramose logistics (intermediary)	Be mainly branched chain alkane; Also comprise ring compound, aromatic hydrocarbon	The b-paraffinic hydrocarbons
				3	Be rich in the ramose logistics	It mainly is methyl ramose paraffinic hydrocarbons	The b-paraffinic hydrocarbons
4	Be rich in ramose logistics (olefinic)	It mainly is methyl ramose paraffinic hydrocarbons; The amount of methyl ramose alkene is as up to about 20%; Also can there be two olefinic impurities	B-paraffinic hydrocarbons/b-alkene
				5	Modified alkylbenzene	It mainly is methyl ramose alkylbenzene	The modified alkylbenzene of Fig. 1 method preparation by having alkylation step
6	Be rich in linear logistics	Be mainly linear paraffinic hydrocarbons	The l-paraffinic hydrocarbons
				7	Discharge logistics (ring-typeization	Ring compound, aromatic hydrocarbon, ethyl and

	Compound/aromatic hydrocarbon)	More senior ramose paraffinic hydrocarbons
				8	Recycle stream	Be mainly methyl ramose paraffinic hydrocarbons	The b-paraffinic hydrocarbons
9	The hydrocarbon charging	Jet/kerosene part is preferably from light crude oil	B-paraffinic hydrocarbons/l-paraffinic hydrocarbons
				10	Be rich in ramose logistics (intermediary)	Be mainly methyl branch and linear paraffinic hydrocarbons	B-paraffinic hydrocarbons/l-paraffinic hydrocarbons
11	Be rich in the ramose logistics	Be mainly methyl branched chain alkane	The b-paraffinic hydrocarbons
				12	Be rich in ramose logistics (olefinic)	It mainly is methyl ramose paraffinic hydrocarbons; The amount of methyl ramose alkene is as up to about 20%	B-paraffinic hydrocarbons/b-alkene
13	Modified alkylbenzene	It mainly is methyl ramose alkylbenzene	The modified alkylbenzene of Fig. 2 method preparation by having alkylation step
				14	Discharge logistics (ring compound/aromatic hydrocarbon)	Ring compound, aromatic hydrocarbon, ethyl-and more senior ramose paraffinic hydrocarbons
15	Be rich in linear logistics	Be mainly linear paraffinic hydrocarbons	The l-paraffinic hydrocarbons
				16	Recycle stream	Be mainly methyl branched chain alkane	The b-paraffinic hydrocarbons
17	The hydrocarbon charging	Jet/kerosene part is preferably from light crude oil	B-paraffinic hydrocarbons/l-paraffinic hydrocarbons
				18	Be rich in the ramose logistics	Be mainly methyl branch and linear paraffinic hydrocarbons	B-paraffinic hydrocarbons/l-paraffinic hydrocarbons
19	Be rich in ramose logistics (olefinic)	Be mainly methyl branch and linear paraffinic hydrocarbons; Must have some linear and methyl ramose alkene	B-paraffinic hydrocarbons/l-paraffinic hydrocarbons/b-alkene/l-alkene
				20	The alkylbenzene of linear and modification	Be mainly methyl branch and linear alkyl benzene	The alkylbenzene mixture of the linear and modification by Fig. 3 method preparation
21	Discharge logistics	Ring compound, aromatic hydrocarbon, ethyl and more senior ramose paraffinic hydrocarbons
				22	Recycle stream	Be mainly methyl branch and linear paraffinic hydrocarbons	B-paraffinic hydrocarbons l-paraffinic hydrocarbons

23	The hydrocarbon charging	The mixture of branched chain alkane and ring compound and aromatic hydrocarbon is derived from conventional LAB equipment waste liquid, as MOLEX _Waste liquid	The b-paraffinic hydrocarbons
				24	Be rich in the ramose logistics	Be mainly methyl ramose paraffinic hydrocarbons	The b-paraffinic hydrocarbons
25	Be rich in ramose logistics (olefinic)	It mainly is methyl ramose paraffinic hydrocarbons; The amount of methyl ramose alkene is necessary for as up to about 20%	B-paraffinic hydrocarbons/b-alkene
				26	The alkylbenzene of modification	It mainly is methyl ramose alkylbenzene	Modified alkylbenzene by the preparation of Fig. 4 method
27	Discharge logistics	Ring compound, aromatic hydrocarbon, ethyl and more senior ramose paraffinic hydrocarbons
				28	Recycle stream	It mainly is methyl ramose paraffinic hydrocarbons	The b-paraffinic hydrocarbons
29	The hydrocarbon charging	F.T. gasoline, senior cut; Split product from loose alkane; Split product from Flexicoker or Fluidcoker	B-alkene/l-alkene/b-paraffinic hydrocarbons/l-paraffinic hydrocarbons
				30	Be rich in ramose logistics (intermediary)	Be mainly methyl branch and linear alkene; Usually have some linear and methyl ramose paraffinic hydrocarbonss	B-alkene/l-alkene/b-paraffinic hydrocarbons/l-paraffinic hydrocarbons
31	Be rich in the ramose logistics	Be mainly methyl ramose alkene and methyl ramose paraffinic hydrocarbons; Ratio is variable	B-alkene/b-paraffinic hydrocarbons
				32	Be rich in ramose logistics (alkene)	It mainly is methyl ramose paraffinic hydrocarbons; The amount of methyl ramose alkene is as up to about 20%	B-paraffinic hydrocarbons/b-alkene
33	The alkylbenzene of modification	It mainly is methyl ramose alkylbenzene	Modified alkylbenzene by the preparation of Fig. 5 method
				34	Discharge logistics (ring compound/aromatic hydrocarbon)	Ring compound, aromatic hydrocarbon, ethyl-and more senior ramose paraffinic hydrocarbons
35	Be rich in linear logistics (can comprise ring compound/aromatic hydrocarbon)	Be mainly linear alkene and linear paraffinic hydrocarbons	L-alkene/l-paraffinic hydrocarbons
				36	Recycle stream	It mainly is methyl ramose paraffinic hydrocarbons	The b-paraffinic hydrocarbons
37	The hydrocarbon charging	F.T. gasoline, senior cut; Come	B-alkene/l-alkene/b-

		Split product from loose alkane; Split product from Flexicoker or Fluidcoker	Paraffinic hydrocarbons/l-paraffinic hydrocarbons
				38	Be rich in ramose logistics (intermediary)	Branch's alkene, branched chain alkane, ring compound and aromatic hydrocarbon	B-alkene/b-paraffinic hydrocarbons
39	Be rich in the ramose logistics	Be mainly methyl ramose alkene and methyl ramose paraffinic hydrocarbons; Ratio is variable	B-alkene/b-paraffinic hydrocarbons
				40	Be rich in ramose logistics (olefinic)	It mainly is methyl ramose paraffinic hydrocarbons; The amount of methyl ramose alkene is as up to about 20%	B-paraffinic hydrocarbons/b-alkene
41	The alkylbenzene of modification	It mainly is methyl ramose alkylbenzene	Modified alkylbenzene by the preparation of Fig. 6 method
				42	Be rich in linear logistics	Be mainly linear alkene and linear paraffinic hydrocarbons	L-alkene/l-paraffinic hydrocarbons
43	Discharge logistics (ring compound/aromatic hydrocarbon)	Ring compound, aromatic hydrocarbon, ethyl-and more senior ramose paraffinic hydrocarbons
				44	Recycle stream	It mainly is methyl ramose paraffinic hydrocarbons	The b-paraffinic hydrocarbons
45	The hydrocarbon charging	F.T. gasoline, senior cut; Split product from loose alkane; Split product from Flexicoker or Fluidcoker	B-alkene/l-alkene/b-paraffinic hydrocarbons/l-paraffinic hydrocarbons
				46	Be rich in the ramose logistics	Be mainly methyl branch and linear alkene; Usually have some linear and methyl ramose paraffinic hydrocarbonss	B-alkene/l-alkene/b-paraffinic hydrocarbons/l-paraffinic hydrocarbons
47	Be rich in ramose logistics (olefinic)	Be mainly linear and methyl ramose paraffinic hydrocarbons; Have some linear and methyl ramose alkene	B-paraffinic hydrocarbons/l-paraffinic hydrocarbons/b-alkene/l-alkene
				48	Modified alkylbenzene	Mainly be methyl branch and linear alkylbenzene	Modified alkylbenzene by the preparation of Fig. 7 method
49	Discharge logistics (ring compound/aromatic hydrocarbon)	Ring compound, aromatic hydrocarbon, ethyl-and more senior ramose paraffinic hydrocarbons
				50	Recycle stream	Mainly be methyl branch and linear paraffinic hydrocarbons	B-paraffinic hydrocarbons l-paraffinic hydrocarbons
51	Thick hydrocarbon charging	The paraffinic hydrocarbons of kerosene scope; 360-500 °F	The b-paraffinic hydrocarbons

		(182-277 ℃) is preferably from the light paraffins raw material	The l-paraffinic hydrocarbons
				52	Light cut (being not used in preparation OXO alcohol or modification LAB)	Light cut-as 360 is to the product cut
53	Heavy cut (being not used in preparation OXO alcohol or modification LAB)	Heavy cut-cut product to 530 from the top
				54	Be rich in ramose logistics (alkene) (dialkene removal)	The amount of main methyl ramose paraffinic hydrocarbons and methyl ramose alkene for as up to about 20% (not having diolefine and/or aromatic substance substantially)	B-paraffinic hydrocarbons b-alkene
55	Be rich in ramose logistics (alkene) (dialkene removal)	Be mainly methyl ramose alkene	B-alkene
				56	The one-level OXO alcohol of modification	Be mainly one-level OXO alcohol and a small amount of paraffinic hydrocarbons of modification	The one-level OXO alcohol of modification
57	The one-level OXO alcohol of modification (no material capable of circulation)	The one-level OXO alcohol of modification	The one-level OXO alcohol of modification
				58	Thick modification one-level OXO alcohol	Be mainly the pure and mild α of one-level OXO of modification-, omega-diol and a small amount of paraffinic hydrocarbons	The one-level OXO alcohol of modification
59	The alkylbenzene of modification and paraffinic hydrocarbons	It is pure and mild up to about 30% modified alkylbenzene to be mainly the one-level OXO of modification	The alkylbenzene of b-paraffinic hydrocarbons modification
				60	The one-level OXO alcohol and the paraffinic hydrocarbons of modification	Be mainly methyl ramose paraffinic hydrocarbons and up to about 25% modification one-level OXO alcohol	The one-level OXO alcohol of b-paraffinic hydrocarbons modification
61	Linear and methyl ramose alkene in the paraffinic hydrocarbons	Be mainly the amount of alkene of the alkane of linear alkane and methyl branch, linear alkene and methyl branch up to about 20% (substantially not having alkadienes and/or aromatic compounds) (linear compound dilutes branch's compound effectively)	B-paraffinic hydrocarbons l-paraffinic hydrocarbons b-alkene l-alkene

62	Linear and methyl ramose alkene	Be mainly linear alkene and methyl ramose alkene	B-alkene l-alkene
				63	The mixture of the pure and mild conventional OXO alcohol of the one-level OXO of modification	Be mainly one-level OXO alcohol and a spot of paraffinic hydrocarbons of the conventional pure and mild modification of OXO	The linear OXO alcohol of modification one-level OXO alcohol
64	The another kind of mixture of the pure and mild conventional OXO alcohol of the one-level OXO of modification	Be mainly the one-level OXO alcohol of the pure and mild modification of conventional OXO, do not have a small amount of paraffinic hydrocarbons	The linear OXO alcohol of modification one-level OXO alcohol
				65	The mixture of the pure and mild conventional OXO alcohol of modification one-level OXO in the paraffinic hydrocarbons	Be mainly the conventional OXO alcohol (OXO by linear raw material reacts the one-level OXO alcohol type that forms) of linear paraffinic hydrocarbons and methyl ramose paraffinic hydrocarbons and about at the most 25% and the one-level OXO alcohol of modification	The linear OXO alcohol of one-level OXO alcohol of b-paraffinic hydrocarbons l-paraffinic hydrocarbons modification
66	The mixture of modified alkylbenzene in the paraffinic hydrocarbons and linear alkyl benzene	Be mainly the linear alkyl benzene and the modified alkylbenzene of linear paraffinic hydrocarbons and methyl ramose paraffinic hydrocarbons and about at the most 30%	B-paraffinic hydrocarbons l-paraffinic hydrocarbons modified alkylbenzene l-alkylbenzene

It is to illustrate but not limitation of the invention that the various hydrocarbon chargings of giving an example in above-mentioned table should be considered as certainly.Can use any other suitable hydrocarbon charging.For example, the split product of petroleum wax that comprises the split product of Fischer-Tropsch wax.These waxes from lubricating oil distillation part and low relatively paramount be about 72 ℃, melt in the 50 ℃ according to appointment-Yue 70 ℃ temperature range, and contain about 36 carbon atoms of the 18-that has an appointment.These waxes preferably contain the various cyclic alkane of 50%-90% normal alkane and 10%-50% monomethyl ramose alkane and low levels.These split product chargings especially can be used in the alternative embodiment of the present invention (as will be as described in after this, and seeing and be set forth in by SRI that Menlo Park is in " ChemicalEconomics Handbook " that California publishes).For example referring to " Waxes ", S595.5003 L, nineteen ninety-five publishes.Paraffin wax is also seen and is set forth in Kirk Othmer ' s Encyclopedia of ChemicalTechnology, the 3rd edition (1984), 24 volumes." Waxes " referring to the 473rd page of place.The alternative hydrocarbon charging of any equivalence or more preferably the short chain Equivalent in the C10-C20 scope and on chain any position have suitable monomethyl branch, for example those also suit from the Fisher-Tropsch synthetic.

Hydrocarbon charging herein can contain the N.O.S. impurity of different amounts.Some preferred hydrocarbon charging (if especially derived from sulfur-bearing and/or nitrogenous part) adopts conventional desulfurization or " removing NOS " technology to carry out desulfurization and/or discharge nitrogenous substances.

Thereby can separating before being used for present method, hydrocarbon charging herein make a large amount of hydrocarbon be used for preparing modified alkylbenzene and/or modification one-level OXO alcohol most effectively with certain chain lengths and/or degree of branching.For example, although do not particularly point out in the drawings, but should need to adopt two kinds of paraffinic hydrocarbons cuts to be used for two kinds of substantially parallel methods from kerosene, each comfortable this is described, thereby a kind of alkylation stage that comprises forms modified alkylbenzene, a kind ofly comprises that an OXO stage forms the one-level OXO alcohol of modification.In such dual mode, usually can preferably adopt the lower cut of total carbon number to prepare alkylbenzene (for example being rich in the cut of C11-C13 hydrocarbon), the part that heavier cut of while for example is rich in the C14-C17 hydrocarbon can be used for preparing the OXO alcohol of modification.The method that can replace comprises alkylbenzene and/or the OXO alcohol that adopts a plurality of hydrocarbon streams or cut to be used for parallel preparation modification and non-modification (routine).The fractionation by adsorption step

Generally speaking, the isolation technique in the inventive method step depends at porous medium and/or adopts on the clathrating agent and adsorbs.The patent that has milestone significance on fractionation by adsorption is US 2,985,589, and it has described the process condition that is applicable to herein various device, adsorption bed and temperature and pressure usually.This patent is not described the improvement of various keys, and especially for being connected of special isolating pore size and each step, and this is a partial content of the present invention.

Generally speaking, each fractionation by adsorption step can be carried out in gas phase or liquid phase, can adopt and also can not adopt as at those the industrialized processing unitss described in the background information of the present invention.

Generally speaking, the porous medium that is used as sorbent material can carry out drying, also can not carry out drying.Embodiment preferred comprises that wherein sorbent material is through super-dry and contain those that are lower than about 2% moisture.

Strippant or displacer can be used or do not used to any fractionation by adsorption step according to the present invention.Generally speaking, can use any desorption apparatus such as transformation or other device.Yet preferably use this strippant, in other words, solvent exchange is the preferred method that desorbs in a kind of porous medium that logistics is used from here.Suitable strippant or displacer comprise various low-molecular-weight n-paraffin, as heptane, octane etc., or polarity strippant such as ammonia.Be understood that, this well-known, be conventional strippant fully, no matter whether it exists, and all can not be included in any logistics or its various compositions of explanation in this prescribing method clearly, and can not adopt on demand and circulate at the strippant circulation step shown in Fig. 1-18.

In the methods of the invention, the stage (a) can be used the MOLEX of UOP ^_Processing step, difference are that the inventive method must have at least one and adopt its aperture to carry out fractionation by adsorption greater than the porous material of the zeolite pore that is generally 5 dusts used in the production of linear alkyl benzene.In above-mentioned Surfactant Science Series the 56th volume (comprising for example 5-10 page or leaf), MOLEX was discussed ^_Various gas phase process such as Union Carbide ' s IsoSiv method (referring to identical reference) also are useful, but not too preferred.

For MOLEX ^_The used herein any form of the equipment of method and operational condition all is well-known; For example, describe the whole bag of tricks and various logistics thereof in detail, comprise raffinate and sorbent material at the 9th page of place referring to above-mentioned reference.Porous medium (wide aperture type)

Required porous medium is the wide aperture type in stage (a) herein.The aperture that " wide aperture " specifically refers to porous medium is sufficiently big so that hold back the linear alkene of monomethyl ramose or paraffinic hydrocarbons and dimethyl branch or linear alkene of trimethylammonium ramose or paraffinic hydrocarbons (except the gem-dimethyl hydrocarbon), but sufficiently little so that gem-dimethyl, ethyl and more senior ramose hydrocarbon and ring-type (as 5-, 6-unit ring) and aromatic hydrocarbon are refused outside to small part.This sufficiently big so that holding back the pore size of the methyl branch hydrocarbon of sufficient quantity is not used in during conventional linear alkyl benzene produces, and with more common 4-5 dust pore size zeolite facies than being used for any commercial run hardly.Wide-aperture porous medium is for being used for Fig. 1-7 those in indicating the adsorption separation unit of " SOR 5/7 ".

Therefore, herein in the stage (a) the minimum-value aperture size of main porous medium greater than the required pore size of linear acyclic hydrocarbous selective adsorption, promptly surpass and be used for those pore sizes that conventional linear alkyl benzene is produced, described pore size is no more than about 20 dusts, more preferably no more than about 10 dusts, most preferably average out to surpasses about 5 dusts to about 7 dusts.When appointment was used for herein the minimum-value aperture size of so-called " wide aperture " porous medium, we should understand that this material has oval-shaped aperture usually, were 4.4 * 6.7 dusts (average out to 5.55 dusts) as the pore size of SAPO-11.Referring to S.Miller, Micropoms Materials, the 2nd volume, 439-449 page or leaf (1994).When with the zeolite facies of the zeolite of this material and " small-bore " such as 4-5 dust uniform pore size relatively the time, when carrying out size relatively the time, agreement herein is to look oval-shaped mean sizes or bigger oval size one is less oval size in no instance.Therefore the pore size of defined herein SAPO-11 material is the zeolite greater than 5 dusts, uniform pore size.

The main porous medium with larger aperture can be zeolite (pure aluminium silicate) in stage (a) herein, also can be nonzeolite.

Suitable nonzeolite comprises various silicon aluminium phosphate salt, especially SAPO-11, though if if mean pore size greater than about 5 dusts or have oval aperture and wherein at least one oval size surpass 5 dusts, then also can use other silicon aluminium phosphate salt.

Another technology that is applicable to fractionation by adsorption herein is the sorption technology of pyrolytic SARAN (producing as the NetherlandsApplication NL 7111508 that publishes according on October 25th, 1971) for adopting pyrolytic poly-(vinylidene chloride).The sieve diameter of preferred material is the 4-7 dust.When using this material, will use the pore size that surpasses about 5 dusts as main sorbent material.Use organo-metallic-grafted mordenite and other grafted zeolite as the porous medium in the stage (a)

The present invention also comprises useful especially embodiment, and wherein the fractionation by adsorption in stage (a) comprises the separating step that at least one adopts organo-metallic-grafted mordenite.Being particularly suitable as herein, the porous medium of " wide aperture " is grafting mordenite such as tin grafted mordenite.Reach similarly and the present invention includes a kind of method under the situation more generally, it comprises using the grafted mordenite to be used for producing detergent surfactant and any corresponding tensio-active agent and passing through uses the prepared life products of these concrete porous mediums in any above-mentioned each method.EP 559,510 A9/8/93 that incorporate this paper referring to entire chapter by reference into.The professional can select the grafting mordenite (can be clear that from embodiment) of these EP 559,510 so that be used for linear and monomethyl ramose hydrocarbon are separated from gem-dimethyl and poly-methyl hydrocarbon with the form of the best.

Other grafting zeolite that can be used as porous medium herein comprises that also entire chapter incorporates those zeolites of the US 5,326,928 of this paper by reference into.In this embodiment of the present invention, especially preferably will following two steps and be single method: the above-mentioned grafting mordenite of use and in step (c) (the other herein alkylation step that partly is defined as), use H-mordenite during stage (a) to the small part dealuminzation.

On this basis, adopt US 5,326, the method assembly (module) that contains graft component and make up with the preferred alkyl step that defines described herein in 928 term, the present invention also comprises the method for the alkylbenzene sulfonate that is used to prepare modified alkylbenzene and/or modification, and described method comprises: (a) at least one will contain and have in various degree in the hydrocarbon charging of molecule of 9-14 carbon atom that ramose aliphatic chain alkane separation becomes at least a less ramose (the linear and monomethyl that comprises, more optional dimethyl ramose) first waste liquid and at least a stage that comprises second waste liquid of more ramose paraffinic hydrocarbons (trimethylammonium and more senior-ramose paraffinic hydrocarbons and optional ring-type and/or aromatic impurities) of paraffinic hydrocarbons; Described separation comprises makes hydrocarbon charging and at least one comprise that at least a microporous solids that has grafting organometallic compound (its quantity and shape are enough to obtain selecting to enter less ramose paraffinic hydrocarbons but the more unapproachable micropore of the paraffinic hydrocarbons of multiple-limb) in its hole is (as at US 5, define in 326,928) adsorption bed contact; (b) at least one is the less alkylating stage of ramose waste liquid in stage (a), preferably carries out in the internal (position) isomer selectivity is the alkylating of 0-40, more preferably be taken to the small part dealuminzation, to the acid H-mordenite of small part as catalyzer; (c) at least one adopts any conventional sulphonating agent that the product in stage (b) is carried out the sulfonated stage.Can in and the modified alkylbenzene sulfonic acid of gained and be attached in the cleaning product (as described in other parts herein).

In the stage of the inventive method (a), the form of the preferred zeolite that uses or other porous medium should make the chemical reaction that can not promote raw material, as cracking, polymerization etc.Therefore, in the stage (a), preferably avoid using acid zeolite.Referring to after this alkylation catalyst in contrast, wherein preferably to small part tart form.Porous medium (smaller aperture due type)

The optional stage (a) that can be used for herein of the zeolite of smaller aperture due for example is denoted as used those of the adsorption separation unit of " SOR 4/5 " in Fig. 1,2,5,6, their are selected the linear hydrocarbon of absorption and do not adsorb methyl-ramose hydrocarbon.This porous material is well-known, and comprises that for example pore size is the scolecite of 4-5 dust.This material is also at US 2,985, obtains further instruction in 589, and is those materials that present industry is used for production line shape alkylbenzene.Porous medium (as OLEX_ or similarity method)

When the one-level OXO of preparation modification herein alcohol, can preferably in the stage (C), implement the olefin/paraff iotan separating step to concentrate monoene.Referring to " SOR O/P " among the figure and the stage (C) in claims.The porous medium that is fit to that is used for this stage comprises X zeolite or the zeolite Y that copper is handled or silver is handled.Referring to as US 5,300,715 or US 4,133,842 (quoting) at this.Also referring to US 4,036,744 and US 4,048,111.Perhaps, the entire method that is called OLEX_ that can obtain to provide is provided UOP Corp. (technology registrant).Clathration

As known in the prior art, can use the urea cage to close herein in the stage (a) so that n-paraffin is separated from branched chain alkane.For example referring to SurfactantScience Series, Marcel Dekker, N.Y.,, the 56th volume, 9-10 page or leaf and wherein each reference in 1996.Also can be referring to " comprising the production of the washing composition of zeolite builders and other novel material ", Ed.Sittig., Noyes Data Corp., 1979,25-30 page or leaf, especially entire chapter were incorporated the US 3 of this paper by reference into, 506,569 (it adopts solid urea but does not have the chloro-hydrocarbons solvent).Can adopt more general but not too preferably according to US 3,162,627 method.Dehydrogenation

Generally speaking, the dehydrogenation of alkene in the inventive method or olefin/paraff iotan mixture can adopt any well-known dehydrogenation catalyst system to realize, these systems comprise each reference of Surfactant Science Series that those are set forth in the background information to be quoted from and are set forth in " comprising the production of the washing composition of zeolite builders and other novel material ", Ed.Sittig., NoyesData Corp., New Jersey, those systems in 1979 and other dehydrogenation catalyst system, for example those Industrial products that can from UOP Corp., buy.Dehydrogenation can be carried out in the presence of hydrogen, usually there is a kind of noble metal catalyst (as DeH-5, DeH-7, the DeH-9 that can from UOP, buy), though can use the dehydrogenation systems such as the zeolite/air system (not having precious metal) of alternative non-hydrogen, non precious metal.

More particularly, the available dehydrogenation catalyst comprises the catalyzer (as the US 5,012 that incorporates this paper by reference into, described in 027) that is carried on the aluminum oxide that contains Sn and has Pt:0.16%, Ir:0.24%, Sn:0.50% and Li:0.54% herein.When this catalyzer and C9-C14 alkane mixture (believing) for linear 500 ℃ with 0.68atm under obtain olefin product (turning round 38 hours) with 90.88% selectivity and 11.02% transformation efficiency when contacting, we believe its quite be applicable to paraffinic hydrocarbons herein be rich in the ramose logistics to the small part dehydrogenation.Also referring to US 4,786,625, EP 320,549 A1 6/21/89; People such as Vora, Chem.AgeIndia (1986), 37 (6), 415-18 page or leaf.

As mentioned above, dehydrogenation can be complete dehydrogenation, also can be the part dehydrogenation, and situation more generally is the part dehydrogenation.When carrying out the part dehydrogenation, this step obtains the mixture of alkene (as be about 10%, these data only are used for explanation, therefore should not be considered as restriction) and institute's equilibrated unreacted paraffins.This mixture is a kind of suitable charging for the alkylation step of the inventive method.

Other available dehydrogenation systems that is easy to be fit among the present invention comprises US 4,762, those of 960 (incorporating this paper herein by reference into), it discloses dehydrogenation catalyst that contains Pt family metal with modified metal, basic metal, alkaline-earth metal or its mixture of being selected from Sn, Ge, Re and various mixtures thereof and specific refractory oxide carrier.

Useful herein various alternative dehydrogenation catalyst and condition comprise US 4,886, those in 926 and US5,536,695.Alkylation

The important embodiment of the present invention also comprise by the slight ramose paraffinic hydrocarbons of isolating enrichment is gone linearizing and to described remove linear alkene or olefin/paraff iotan mixture to the small part dehydrogenation, carry out alkylation.The aromatic hydrocarbon that employing is selected from benzene, toluene and composition thereof carries out alkylation.The selection of internal (position) isomer selectivity and alkylation step

It is 0-40, preferred 0-20, the more preferably alkylation step of 0-10 that the inventive method embodiment preferred requires the internal (position) isomer selectivity.For any given alkylation process step, it is that 10: 1 benzene carries out the alkylation test by the 1-dodecylene and measures that defined herein internal (position) isomer selectivity or " IIS " adopt mol ratio.In the presence of alkylation catalyst, carry out alkylating so that transform at least 90% dodecylene and generate a phenyl dodecane of at least 60%.Following then definite internal (position) isomer selectivity:

Wherein quantity is the quantity (weight) of product; The quantity of final phenyl dodecane is the summation of 2-phenyl dodecane and 3-phenyl dodecane quantity, add 3-phenyl dodecane and add 4-phenyl dodecane and add the summation that 5-phenyl dodecane adds 6-phenyl dodecane and the total amount of phenyl dodecane is a 2-phenyl dodecane, wherein said quantity is determined by any known analytical technology such as vapor-phase chromatography that is used for alkylbenzene sulfonate.Referring to Analytical Chemistry, November, nineteen eighty-three, 55 (13), 2120-2126 page or leaf, people such as Eganhouse, " long-chain alkyl benzene in environmental sample " by argentation thin layer chromotography-high resolution gas chromatography and vapor-phase chromatography/mass spectroscopy.When calculating IIS according to following formula, each quantity is divided by, 1 deduct the result and multiply by 100 then.What will of course be appreciated that is, the concrete alkene that is used to identify or tests any given alkylation step suitability is a contrast, it can be compared herein alkylation step with the known various alkylation steps that are used to prepare linear alkyl benzene, and makes the professional can determine whether a given known alkylation step can be used for forming in each processing step series of the present invention.In implementing the inventive method, be used for the hydrocarbon charging of the actual alkylation step that is adopted yes being determined according to each processing step of its front.Note also that simultaneously why all commercial runs that are used to produce LAS at present are different from the preferred embodiments of the invention, unique basis is based on the IIS that alkylation step adopts.For example, based on the IIS of the various LAS methods of aluminum chloride, HF etc. all not in the specified scope of the inventive method.On the contrary, some see that the several alkylation steps that are set forth in the document but are not applied in the alkylbenzene sulfonate industrial production at present have suitable IIS, and can be used among the present invention.

In order to assist the professional to determine IIS better and to determine whether a given alkylation step is applicable to the object of the invention, below be to determine IIS example more specifically.

As mentioned above, the alkylation of carrying out benzene by the 1-dodecylene is that the mol ratio at benzene and 1-dodecylene is to carry out for 10: 1 times, and alkylating carries out in the presence of alkylation catalyst so that transform 90% dodecylene and generate a phenyl dodecane of 60% at least at least.Generally speaking, alkylation test must be less than 200 hours and temperature of reaction is about-15 ℃ to being about 500 ℃, preferably being about under 20-500 ℃ the condition and carrying out in the reaction times.Pressure and catalyzer are wider with respect to the range of concentrations of 1-dodecylene.Except benzene, in the alkylation test, do not use solvent.Can be identified for the whole bag of tricks condition of the IIS of catalyzer or alkylation step based on this document.The professional can adopt usually based on the suitable condition that is used for alkylating various detailed data in a large number.For example, if can use AlCl herein ₃Alkylation, then determined various suitable process conditions are, at 20-40 ℃ of following 1-dodecylene and 5% (mole is with respect to the 1-dodecylene) AlCl ₃Reaction is 0.5-1.0 hour in batch reactor.This test shows, AlCl ₃Alkylation step is not suitable in the inventive method.IIS should be about 48.In another embodiment, adopt HF should be about 60 as the IIS of the suitable alkylation experiment of catalyzer.Therefore, AlCl ₃Alkylation and HF alkylation be not within category of the present invention.For the zeolite such as dealuminium mordenite of intermediate pore size, be applicable to that the process condition of determining IIS is that 10: 1 1-dodecylene and benzene were with 30 hours by making mol ratio for example ^-1WHSV be about 200 ℃, pressure in temperature of reaction and be about this mordenite catalyst of flowing through under the 200psig, so for mordenite catalyst, can obtain being about 0 IIS.The temperature and pressure (also can referring to after this each detailed embodiment of the inventive method) that is used for exemplary mordenite alkylation test can more generally be used to test various zeolites and other shape is selected alkylation catalyst.Adopt catalyzer should obtain being about 18 IIS as H-ZSM-4.Clearly, all obtained the acceptable IIS of the present invention, preferred mordenite by dealuminium mordenite and the catalytic alkylation of H-ZSM-4.

Do not want to be entangled in theory, we believe that the low-IIS alkylation step that adopts H-mordenite herein to be implemented can adopt is rich in the ramose hydrocarbon benzene is carried out alkylation, but it is also quite useful for putting upside down the methyl ramose position that (scrambling) be attached on the hydrocarbon chain.Alkylation catalyst

Selection by strictness control alkylation catalyst can obtain IIS required in the alkylation process step.Be easy to determine that a large amount of alkylation catalysts is unfavorable.Various unfavorable alkylation catalysts comprise DETAL ^_HF on method catalyzer, aluminum chloride, HF, the zeolite, fluoridize zeolite, non-acid calcium mordenite and many other catalyzer.In fact, we find up to now, do not have a kind of suiting in the alkylating alkylation catalyst that is used for industrial production washing composition linear alkyl benzene sulfonate at present.

On the contrary, Shi Yi alkylation catalyst is selected from the moderate acid alkylation catalyst that shape is selected herein, is preferably zeolite.Be preferably selected from mordenite, ZSM-4, ZSM-12, ZSM-20, offretite, sarcolite and beta-zeolite at this zeolite that is used for the catalyzer of alkylation step (step (b)) to the small part acid form.More preferably the zeolite in the step (b) (alkylation step) is the form of acid basically, and be included in the granules of catalyst that comprises conventional tackiness agent, wherein said granules of catalyst comprises at least about 1%, more preferably at least 5%, the more preferably described zeolite of 50%-about 90% usually.

More in general, suitable alkylation catalyst is normally to the small part crystalline, is more preferably not comprise that basically tackiness agent or other are used to form material crystalline of granules of catalyst, aggregate or composition.In addition, this catalyzer is normally to the small part tart.For example, the mordenite of Jiao Huan Ca-form is unfavorable fully, and the mordenite of H-form suits.After this this catalyzer is used in and is appointed as in the alkylation step of step (b) in claims: it is corresponding to the step 7 among Fig. 1.

Its aperture feature of zeolite that can be used in the alkylation of the present invention can be rounded basically, as having the uniform pore size of about 6.2 dusts in cancrinite, or preferably can be ellipse in a way, as the situation in mordenite.We are understood that, under any circumstance, the main aperture size of various zeolites that is used as catalyzer in the inventive method alkylation step is preferably between about 6 Ai-Yue 7 dusts between the zeolite (as ZSM-5 and ZSM-11) of large aperture zeolite (as X and Y zeolite) and smaller aperture due size.In fact we had tried ZSM-5, but found that it can't operate in the present invention.The pore size size of some zeolite and crystalline structure are described in more detail in by (1978 and many second editions) of Structure Commission of theInternational Zeolite Association publication with by Polycrystal Book Service, Pittsburgh is in the zeolite structure type collection of illustrative plates (W.M.Meier and D.H.Olson) of Pa. distribution.

The zeolite that can be used in the inventive method alkylation step has at least 10% usually by the occupied positively charged ion position of the ion except basic metal or alkaline-earth metal.Common but infinite displacement ion comprises ammonium, hydrogen, rare earth metal, zinc, copper and aluminium.In the middle of this series, particularly preferably be ammonium, hydrogen, rare earth metal or its various combinations.In a preferred embodiment, usually zeolite is converted into the form (obtaining the form of hydrogen by calcining) that is mainly hydrogen by adopting hydrogen ion precursor such as the ammonium ion former basic metal that pre-exists of displacement or other ion.Utilize well-known ion exchange technique, can carry out this exchange easily by zeolite is contacted with the solution of ammonium salt such as ammonium chloride.In some preferred embodiment, the metathetical degree should obtain wherein at least 50% positively charged ion position by the occupied zeolitic material of hydrogen ion.

Zeolite can carry out various chemical treatments, comprises alumina extraction (dealuminzation) and combines with one or more metal component (the particularly metal of family's II B, III, IV, VI, VII and VIII).We it will be appreciated that also zeolite can be heat-treated on demand in some cases, comprise feeding steam or calcining in air, hydrogen or rare gas element such as nitrogen or helium.

Suitable modification is handled the atmosphere that need make zeolite and temperature be about 250 ℃-1000 ℃, contain about 100% steam of the 5%-that has an appointment and is contacted and make it obtain steaming.Steaming can continue about 0.25-about 100 hours, and can carry out under the atmospheric pressure to hundreds of being lower than a normal atmosphere.

When implementing alkylation step required for the present invention, the crystalline zeolite of above-mentioned medium pore size can be attached to another kind of material such as tackiness agent or tolerable temperature with the inventive method in the matrix of used various conditions.This substrate material comprises synthetic or natural substance and various inorganic materials such as clay, silicon-dioxide and/or metal oxide.Substrate material can be the form of various gels, comprises the mixture of silicon-dioxide and metal oxide.The latter can be natural form, also can be the form of gel, or gelatinous precipitate.Can comprise montmorillonite and kaolin series with the natural clay of combination of zeolites, this series comprises various inferior wilkinites and kaolin, Dixie, McNamee-Georgia and Florida clay as is well known, or other wherein main inorganic component those materials that are halloysite, kaolinite, dickite, nakrite or anauxite.This clay can the primary state uses, also can be the form of original exploitation or calcine at the very start, acid treatment or chemical modification.

Except above-mentioned materials, the zeolite of medium pore size used herein can with porous substrate material such as aluminum oxide, silica-alumina, silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia and silica-titania and triple combination such as compositions such as silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-magnesium oxide and silica-magnesia-zirconium white.This matrix can be common agglomerative form.The segmentation zeolite and the relative proportion of inorganic oxide gel matrix can alter a great deal, the content of zeolite can be mixture about 99% (weight) of about 1%-, be more typically about 80% (weight) of about 5%-.

Comprise that some can be used for the silicon-dioxide of one group of zeolite of alkylation step herein: the ratio between the aluminum oxide is at least 10: 1, preferably at least 20: 1.The silicon-dioxide of indication in this manual: the ratio between the aluminum oxide is the ratio of structure or skeleton, that is to say the ratio of SiO4 and AlO4 tetrahedron.This ratio can be with the silicon-dioxide of determining by various physics and chemical process: the ratio of aluminum oxide different and different.For example, total chemical analysis may comprise with cationic form and being connected on the acid sites on the zeolite, takes this to obtain low silicon-dioxide: the aluminum oxide ratio.Similarly,, this ratio determines, if then cationic aluminium stops ammonium ion exchange will obtain low ammonia titration to acid sites if being thermogravimetry (TGA) by deamination.These disparities will cause the consequence that quite bothers when using some to handle dealuminzation method described as follows (obtaining zeolite structured outer aluminum ion).Thereby should note guaranteeing silicon-dioxide in the skeleton: the aluminum oxide specific energy obtains correct determining.

Be applicable to that herein beta-zeolite (but not as H-mordenite so preferred) is disclosed in United States Patent (USP) the 3rd, 308, in No. 069, the document describes this zeolite and preparation method thereof in detail.This zeolite of acid form also is commercially available, as the ZeocatPB/H available from Zeochem.

When preparation zeolite in the presence of organic cations, these zeolites are catalysis inactive, and this may be because the occupied cause of organic cation that intracrystalline freeboard is come self-forming solution.By in inert atmosphere, heating 1 hour down at 540 ℃, carry out the alkali exchange with ammonium salt then, then under 540 ℃, in air, calcine again and can make its activation.Having organic cation in forming solution may not be absolute necessity for the generation of zeolite; But as if help very much the formation of this specific type zeolite.Sometimes some natural zeolites can be converted into the zeolite of required type by various activation methods and other various processing such as alkali exchange, steam heating, alumina extraction and calcining.Preferred crystallization of zeolites skeletal density (form of dry hydrogen) is not less than about 1.6 gram per centimeters basically ³Dry density for known structure can be from per 1000 dusts ³Silicon and aluminium atom sum calculate and (as be included in by Society of Chemical Industry and publish (London, nineteen sixty-eight) the 19th page of article of being write by W.M.Meier about zeolite structured is described in " Proceedings of the Conference on MolecularSieves; London, in April, 1967 ").With reference to of the discussion of this paper for crystal framework density.Can also be with reference to United States Patent (USP) the 4th, 016, in No. 218 for the discussion of crystal framework density and the numerical value of some typical zeolites.When zeolite synthesizes with alkali-metal form, can be translated into the form (generally obtain the intermediate of ammonium salts by ammonium ion exchange, the form of calcining ammonium salt then obtains the form of hydrogen) of hydrogen easily.Although we find that the form of zeolite hydrogen can successfully carry out catalysis to reaction, this zeolite also can partly be alkali-metal form.

EP 466,558 have described a kind of alkylation catalyst that also can be used for acidic mordenites type herein, its total Si/Al atomic ratio is 15-85 (15-60), the Na weight content is less than 1000ppm (preferably being less than 250ppm), has content low or that do not have the outer Al kind of network, unit grid (elementary mesh) volume is less than 2,760 nanometers ³

Can be used for preparing the US 5,057,472 of alkylation catalyst herein relate to acid stable contain sodium ion zeolite (preferred mordenite) time dealuminzation and ion-exchange take place (by containing enough NH with 0.5-3 (being preferably 1-2.5) M ₄NO ₃HNO ₃Solution contacts so that the Na ion fully exchanges NH ₄Be achieved with the H ion).The SiO of gained zeolite ₂: Al ₂O ₃Ratio be 15-26 (being preferably 17-23): 1, and preferably calcine so that small part with NH ₄/ H form is converted into the H form.Though be not special needs in the present invention, optional this catalyzer can contain the zeolite after the calcining of family's VIII metal (and optional inorganic oxide) and above-mentioned patent.

Another kind can be used for herein that the acidic mordenite catalyst of alkylation step is disclosed in US4, and in 861,935, it relates to the mordenite with aluminum oxide bonded hydrogen form, and the surface-area of said composition is at least 580 meters ²/ gram.Other can be used for herein the acidic mordenite catalyst of alkylation step and comprises and be set forth in US 5,243,116 and US 5,198,595 in those.Another herein the available alkylation catalyst see and be set forth in US 5,175, in 135, it is that a kind of silica/alumina mole ratio is at least 50: 1, symmetry index and is at least 1.0 (determining by the X-ray diffraction analysis) and porosity and makes total pore volume be the acidic mordenites of about 0.25-about 0.75 for the ratio of the about 0.45cc/g of about 0.18cc/g-and mixing mesopore and macropore volume and total pore volume.

Particularly preferred herein alkylation catalyst comprises the Zeocat that can buy from Zeochem ^TMThe acidic mordenite catalyst of FM-8/25H, the CBV 90A that buys from Zeolyst International and the LZM-8 that from UOP Chemical Catalysts, buys.

The most generally speaking, can use any alkylation catalyst herein, condition is that this alkylation step satisfies optionally various requirement of above-mentioned internal (position) isomer.The distillation of modified alkylbenzene or modification one-level OXO alcohol

According to raw materials used and concrete sequence of steps, the inventive method can be chosen the distillation that comprises modified alkylbenzene or modification one-level OXO alcohol wantonly, for example to remove unreacted starting material, paraffinic hydrocarbons, excessive benzene etc.Can use the distillation plant of any routine.General class of operation is similar to distillating industries linear alkyl benzene (LAB) or the used operation of OXO alcohol.Suitable distilation steps sees that the Surfactant Science Series that is set forth in above-mentioned reference is as in " alkylbenzene sulfonate production review ".Sulfonation/sulfation and aftertreatment (Workup)

Generally speaking, the sulfation of the sulfonation of the modified alkylbenzene in the inventive method or modification one-level OXO alcohol (or their alkoxide) can adopt any well-known sulfonation system to finish, and comprises the Surfactant Science Series of above-mentioned reference " comprising the production of the washing composition of zeolite builders and other novel material " and above-mentioned reference " review that alkylbenzene sulfonate is produced ".Common sulfonation system comprises sulfuric acid, chlorsulfonic acid, oleum, sulphur trioxide etc.Especially preferred sulphur trioxide/air.The sulfonation details that adopts suitable air/sulfur trioxide mixture to carry out is seen the US 3,427,342 that is set forth in Chemithon.Method of sulfonating also extensively is described in " sulfonation technology in the detergent industry ", W.H.de Groot, KluwerAcademic Publishers, Boston, 1991 years.

Can use any post-processing step easily in the methods of the invention.Common operation is to adopt any suitable alkali to neutralize after sulfonation.So employing is selected from the ammonium alkali of sodium, potassium, ammonium, magnesium and replacement and the alkali of various mixtures can carry out neutralization procedure.Potassium helps solvability, and magnesium can improve the soft water performance, and the ammonium that replaces then helps to prepare the various special various tensio-active agents of the present invention.The present invention includes any alkylbenzenesulfonatsurfactants surfactants, perhaps the derivative form of the one-level OXO alcohol of the one-level OXO alcohol of sulfation modification or alkoxide, sulfation modification and the purposes in the life products composition thereof by the inventive method preparation.

Perhaps the tensio-active agent of the present invention of acid form directly can be joined in the acid clean product, or can mix with each cleansing and then neutralize.Back alkylation step

As mentioned above, the inventive method herein comprises the embodiment with the various steps of carrying out afterwards at alkylation step (c).Preferred these steps comprise the product of (d) sulfonation procedure (c); Be selected from following one or more step: (e) product of neutralization procedure (d); (f) step (d) or product (e) are mixed with one or more cleaning product additive materials; Take this to generate cleaning product.The fusion embodiment

In a preferred embodiment, before carrying out described sulfonation procedure, make the modified alkylbenzene that is described step (c) product and linear alkyl benzene fusion by the ordinary method preparation.In another such embodiment, in any one step after described sulfonation procedure, make modified alkylbenzene sulfonates and the linear alkyl benzene fusion for preparing by ordinary method as described step (d) product.In the embodiment of these fusion, the ratio of the modified alkylbenzene of preferred method and linear alkyl benzene is about 10: about 50: 50 of 90-.

Corresponding fusion scheme is applicable to modification one-level OXO alcohol method herein certainly.In addition, can carry out fusion to various types of tensio-active agents or their precursor substance herein.For example, the alkoxide mixture of the modification one-level OXO alcohol of the alkylbenzene of implementer's fusion modification freely and preparation herein, employing oxyethane, propylene oxide etc., sulfates/sulfonates is to final mixture then.In addition, generally speaking, modification OXO alcohol can separate by distillation, various other OXO alcohol types that comprise linear OXO alcohol known in the art, linear OXO alcohol), and the method that this OXO alcohol adulterant is converted into the tensio-active agent that is applicable to washing composition the present invention also comprises with the obtainable herein modification of arbitrary proportion fusion or the pure and mild any known OXO alcohol of ramose OXO (as the branch from about 1: 100 to about 100: 1 (weight):.Other method embodiment

The present invention comprises that also a kind of waste liquid stream that is used for handling from the production of linear alkyl benzene sulfonate surfactant can be used in the cleaning product it, described method comprises that (ⅰ) is separated into the stream that is rich in n-paraffin with isoparaffin to small part and comprises that be rich in isoparaffin (particularly methyl ramose paraffinic hydrocarbons) and its molecular weight at least about 10% isoparaffin are at least about 128 and be no more than about 282 waste liquid stream, wherein said separation comprises that at least one is selected from the clathration of being undertaken by urea and the step of the centrifugation undertaken by sorption, and wherein said each step is necessary in the method that is used for the production of linear alkyl benzene; (ⅱ) by at least one step that is selected from urea clathration and sorption centrifugation to the small part isoparaffin content of the described waste liquid stream of enrichment again; Wherein said step is an additional step and in step (ⅰ) afterwards; (ⅲ) make the step of the stream dehydrogenation of being rich in isoparaffin of described step (ⅱ) to small part.

More generally, we wish that prepared hydrocarbon not only can be used in the alkylbenzenesulfonatsurfactants surfactants as the non-limitative illustration example herein, and can be used in the modified surface promoting agent (as alkyl-sulphate) except alkylbenzene sulfonate.Therefore, the present invention also comprises a kind of method that is used to handle branched chain alkane waste liquid stream, it comprises that (ⅰ) is separated into the stream that is rich in n-paraffin with isoparaffin to small part and comprises the waste liquid stream that is rich in isoparaffin at least about 10% isoparaffin, and wherein said separation comprises that at least one is selected from the clathration of being undertaken by urea and the step of the centrifugation undertaken by sorption; (ⅱ) by at least one step that is selected from urea clathration and sorption centrifugation to the small part isoparaffin content of the described waste liquid stream of enrichment again; Wherein said step is an additional step and in step (ⅰ) afterwards; (ⅲ) make the step of the stream dehydrogenation of being rich in isoparaffin of described step (ⅱ) to small part.

In this embodiment, its the total carbon content of stream that is rich in isoparaffin can be the about C20 of about C10-, and the nonlinear element per molecule of described rich stream on average comprises about 2 methyl chains of about 1-(except the terminal methyl group side chain), the nonlinear element of described rich stream preferably include be less than about 30%, more preferably less than about 10%, also more preferably less than about 1% molecule be less than 50%, preferably be less than the molecule that gem-dimethyl replaces that has about 10%, more preferably less than about 1% with quaternary carbon atom.Embodiment (OXO reaction) in conjunction with carbonylation

As mentioning in the general introduction, the present invention also comprises some embodiments, and they relate to selects to be converted into the modification one-level OXO alcohol that new and useful being used to prepare (alkoxide) vitriol other soluble sulphate, poly-and poly-(alkoxide) with hydrocarbon by some fractionation by adsorption.These just explanations as an example.The modified version of other surfactant types known in the art of being derived by OXO certainly and coming is also included within the present invention.According to the such embodiment of generalized in the summary, preferred method herein has the stage (A) device, and at least one described bed that it comprises, two or more described equipment and at least two described beds, comprise described porous medium and difference of another porous medium amount of described are the ability of the maintenance methyl ramose cycloalphatic hydrocarbon that increases.Yet the preferred described stage (D) comprises an OXO stage in step, and wherein said OXO catalyzer is and phosphine coordinate transition metal (not being iron).

More specifically, in this preferable methods, at least one described bed comprises the porous medium that is generally used for producing linear alkylbenzene; At least one described bed links to each other with described method, be suitable for increasing the ratio of the methyl ramose open chain aliphatic hydrocrbon in the logistics in the described stage (B) by entering described method to small part, and being suitable for reducing the ratio of the linear open chain aliphatic hydrocrbon in the logistics in the described stage (B) by entering described method to small part, described linear open chain aliphatic hydrocrbon is at least partially in being removed with the form that is rich in linear logistics in the described stage (A).

For simplicity, in such process implementing scheme, in the described stage (A), described simulation moving-bed adsorption separation device comprises-described an equipment, condition is that described equipment can be simulated at least two described equipment at least one, the perhaps motion of the described porous medium in two described equipment at least.

Also comprise a kind of method at this, wherein at least one bed, there are two described equipment, they comprise the described porous medium of different elements separately, described at least one bed is subjected to a described device control, described equipment to have minimum 8 outlets separately to be used for simulating described porous medium in described at least one motion separately.Referring to as Fig. 9, wherein cell S OR4/5 comprise a class porous medium (more specific definition in this paper other somewhere), cell S OR 5/7 comprises another kind of type." equipment " is meant and can especially be selected from specific turning valve equipment (detailed content is described in the pointed various patents of " background technology " part).Also referring to Fig. 8, although it has more specifically described the method with alkylation step, it also shows the reasonable arrangement of adsorption separation unit, turning valve and utility appliance in greater detail.Should be understood that at this: adsorption medium and equipment all are known separately; Importantly the selection of equipment with how to be connected them, this is the key that obtains the object of the invention of the excellent pure and mild deriving surface promoting agent of OXO.

Therefore the present invention also comprises class methods of producing OXO alcohol, wherein saidly be rich in linear logistics and be present in the described stage (A), the described stage, (A) comprising: (A-ⅰ) is by the fractionation by adsorption equipment of a described simulation bed, the described hydrocarbon charging of fractionation by adsorption becomes is rich in linear logistics and intermediary is rich in the ramose logistics, and discharges the described linear logistics that is rich in; (A-ⅱ) is by another simulation moving-bed fractionation by adsorption equipment then, the described intermediary of fractionation by adsorption is rich in the ramose logistics to be become and contains the described ramose logistics that is rich in that is rich in branch's open chain aliphatic hydrocrbon that ramose logistics ratio increases with respect to described centre, and described discharge logistics comprises ring-type and/or the aromatic hydrocarbon (with respect to the described ramose logistics that is rich in) that ratio at least increases.

Preferably in this embodiment, all described beds comprise and are not that routine is used to prepare the porous medium of linear alkyl benzene (as being included in the SAPO-11 of cell S OR 5/7 or the molecular sieve that other suitable being used to prepares linear alkyl benzene), adding hole dimension that the described porous medium of described method has and be suitable for increasing the methyl branch in the logistics of the described step (B) by described method and the ratio of linear open chain aliphatic hydrocrbon to small part, is not that described described hydrocarbon linear and methyl ramose hydrocarbon is removed at least partially in the form with the discharge logistics in the stage (A).

In the preparation embodiment of OXO alcohol of the present invention, described hydrocarbon charging comprises methyl ramose paraffinic hydrocarbons at least about 10% (molecular weight be at least 128 and be not more than 282) suitably.Referring to of the other description of other local form of this paper as suitable charging.

In the OXO method, preferably distill thick charging before use herein.For example carry out non-limitative illustration by the distillation unit that begins in method shown in Fig. 9-18.In this embodiment, hydrocarbon charging (when it enters the other parts of described method from distilling the unit) comprises the narrow cut (in the C10-C17 scope) that is not more than three carbon atoms (preferably being not more than two carbon atoms).This cut can be single carbon cut, two carbon cuts, three carbon cuts or comprise the cut such as the one-and-one-half carbon cut of the carbon number of imprecise scope, the example of suitable cut has C11-C13 cut, C14-C15 cut and C15-C17 cut, although do not plan to get rid of other cut such as C16.5 cut.These are appointed as non-integral cut can be by producing as mixing method short and the single carbon number part of length.Therefore the C16.5 cut can wait by mixed C 16 and C17 or by mixed C 14 and C17 and prepare.Preferred cut has narrower carbon number " extension " in mixture.Perhaps, described distillation can just be directly used in olefinic and be rich in branch's logistics to prepare required cut before olefinic is rich in the OXO reaction of branch's logistics.

For implementing purpose, should be understood that: when herein hydrocarbon of distillation, the boiling point of required methyl ramose hydrocarbon is usually less than the linear hydrocarbon with same carbon number.Therefore, will to be rich in total carbon number be 16 methyl ramose isomer (they are that present method is required) to the preferred cut of boiling point between linear C15 and linear C16 paraffinic hydrocarbons.

Extraordinary is that if not unique, for the preparation method of OXO alcohol, described hydrocarbon charging is the fractionation by adsorption paraffinic hydrocarbons derived from linear alkyl benzene preparation method or conventional linear detergent alcohol method.That is to say that the present invention has started all in conjunction with linear alkylbenzene preparation and/or conventional linear detergent alcohol method with after this with all new possible modes of the pure preparation method of OXO that implements.It obtained to charging than good utilisation.In addition, described herein when of the present invention when adopting, can obtain new alkylbenzene and OXO alcohol.Can implement them separately, perhaps can described device rationally be set, exchange with conventional linear alkyl benzene and/or OXO alcohol by adopting step described herein.

In case make the one-level OXO alcohol of modification, certainly it changed into another kind of useful derivative in same apparatus or at another isolating device.For example, present method can have other stage, is selected from successively: (E) product of the sulfation and described stage (D) that neutralize; (F) product in described stage of alkoxide (D); (G) product of alkoxide, sulfation and described stage (D) that neutralize.

In addition, in case make the surfactant derivatives of the above-mentioned type, they can easily all add in the cleaning compositions.Because this purpose is set said apparatus jointly or separated the device of placing, present method can have product and one or more cleaning product additive materials of another step (H)-mixing earlier stage; Form cleaning product thus.

Although can partly find out by background technology, various OXO alcohol known (referring to as Shell and/or Sasol method), suggestion was not adopted the special fractionation by adsorption that specifies herein at OXO before the stage in the past.In addition, there is not suggestion that the nonuseable part (at least aspect the washing composition) of the logistics that provides by the preparation of linear alkyl benzene is provided herein yet.Selection by coarse raw materials or adopt the special fractionation by adsorption stage, or both, the composition of gained OXO alcohol changes with respect to Shell and Sasol method, and make them be highly suitable for the preparation of tensio-active agent, be particularly suited for the application of low wash temperature, high request solvability (closely particle, sheet) or the higher water hardness.All these all have very big economic benefits.According to the variation of the composition of giving OXO alcohol, the present invention also comprises the modification one-level OXO alcohol by any present method preparation.

Equally, the present invention includes the cleaning product that satisfies the needs of consumers by method for preparing, aforesaid method comprises the preparation of special OXO alcohol described herein, is subsequently to comprise the stage of mixing at least a cleaning product additive material component.

In other changed, method herein comprises following method: (D) was preceding in the described OXO stage, makes described stage (B) or product (C) and conventional washing composition olefin; Or wherein said stage (E), (F) or product (G) mix with conventional detersive surfactant.

Although existing wherein, present method can prepare or the alkylbenzene of alternately technological cycle modification and many structures of modification one-level OXO alcohol simultaneously, but this nonrestrictive method according to the present invention further comprises 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 (A); For the alkylbenzene of (crystalline fracture) that prepare modification, described alkylation catalyst has the internal (position) isomer that selectivity is 0-40.Branch comprised to the product route in stage (C)-(D), described alkylation step or described two stages provides equipment.Further specify referring to accompanying drawing.

More broadly, the present invention also comprises washing composition or cleanser compositions, it comprises: (a) significant quantity be selected from following detersive surfactant: alkyl-sulphate, alkyl gathers (alkoxyl group) vitriol, alkyl poly-(alkoxide) and composition thereof, (preferably its amount is at most one mole to the detergent alcohol of the formula ROH of R=C9-C20 in the described tensio-active agent adding R-O-group, more preferably from about one mole), wherein R is the mixture of methyl branch and some straight chain, and described alcohol further is characterized as it and contains at least a Fischer-Tropsch method stage or dimerization or skeletal isomerization stage or alkene and/or paraffinic hydrocarbons supply stage (as the hydroisomerization/cracking by top fractionation by adsorption or other method such as wax, Flexicoking_, Fluidcoking_ etc.) and the product of at least one OXO operation stage; Condition is at least one stage before the OXO operation stage, and existence can effectively increase the fractionation by adsorption stage as the ratio of the methyl ramose alkene of described OXO operation stage charging; (b) help one or more additives that improve the useful performance of composition to small part.

Also comprise washing composition or cleaning compositions at this, it comprises the detersive surfactant that is selected from alkyl-sulphate, poly-(alkoxyl group) vitriol of alkyl, alkyl poly-(alkoxide) and composition thereof of (a) significant quantity, (preferably its amount is at most one mole to the detergent alcohol of the formula ROH of R=C9-C20 in the described tensio-active agent adding R-O-group, more preferably from about one mole), wherein R is the mixture of methyl branch and some straight chain, and described alcohol further is characterized as its any product that comprises above-mentioned modification one-level OXO alcohol preparation method; (b) help one or more additives that improve the useful performance of composition to small part.The cleaning product embodiment

Cleaning product embodiment of the present invention comprises various detergent for washing clothess, dish washing detergent, hard surface cleaner etc.In this class embodiment, modified alkylbenzene sulfonates by the inventive method preparation or be about 0.1%-about 99.9% derived from the tensio-active agent of modification one-level OXO alcohol, be generally about 1%-about 50%, and said composition comprises also that about 0.1%-is about 99.9%, is generally the various cleaning product additive materials of about 1%-about 50%, as cosurfactant, washing assistant, enzyme, SYNTHETIC OPTICAL WHITNER, bleach boosters, activator or catalyzer etc.

The present invention comprises that also it comprises by the cleaning product of the inventive method preparation:

(a) about 0.1%-about 99.8%, be generally up to about 50% as the alkylbenzenesulfonatsurfactants surfactants of this preparation or the alkyl-sulphate of modification one-level OXO alcohol deriving surface promoting agent such as modification, poly-(alkoxyl group) vitriol of modification etc. and

(b) about 0.00001%, be more typically one or more described cleaning product additive materials at least about 1%-about 99.9%.

Because the scope of various additive materials is considerably extensive, so its amount ranges also can be wider.For example, the various washings that can use very low or very high (more rare) content herein are with enzyme such as proteolytic enzyme, amylase, cellulase, lipase etc. and various bleaching catalyst (comprise big lopps type have manganese or all are similar to be can be used for doing washing and the transition metal of cleaning product).

Other cleaning product additive material of Shi Yonging comprises various SYNTHETIC OPTICAL WHITNER herein, especially the type of oxygen bleaching, comprise and adopt this bleach-activating agent activation and catalytic type, cross oxy hexanoic acid or other imino--or the derivative (comprising the lactan type) of the amino bleach-activating agent that replaces as nonanoyl hydroxy benzene sulfonate and/or tetraacetyl ethylene diamine and/or its any derivative or various phthaloyl imino, or be more generally any mixture (especially various acyl derivatives comprise those types of the hydroxy benzene sulfonate that C6-C16 replaces) of wetting ability and/or hydrophobicity bleach-activating agent; Relate to or based on any mentioned before this bleach-activating agent, the various prefabricated peracid of washing assistant, comprise that insoluble type is as comprising zeolite A, the various zeolites of P and so-called maximum aluminium P, with solvable type such as phosphoric acid salt and polyphosphate, any moisture, water-soluble or water-insoluble silicate, 2,2 '-hydroxyl disuccinate, the succsinic acid tartrate, oxyacetate, NTA and many other ether carboxylicesters or citrates, various sequestrants, comprise EDTA, S, S ' EDDS, DTPA and phosphonic acid ester, water-soluble polymers, multipolymer and terpolymer, various soil release polymers, cosurfactant, comprise any known anionic, positively charged ion, nonionic or zwitter-ion type, white dyes, various processing aids such as crisp dose and/or filler, solvent, anti redeposition agent, silicon/silicon dioxide and other froth suppressor, hydrotropic agent, spices or preceding spices (pro-perfume), dyestuff, photobleaching agent, thickening material, single salt and an alkali metal salt comprise its oxyhydroxide as an alkali metal salt based on sodium or potassium, carbonate, supercarbonate and vitriol etc.When mixing with the alkylbenzenesulfonatsurfactants surfactants of the inventive method gained, any cleaning product anhydrous, moisture, water base or that carry solvent is easy to make particulate state, sheet, Powdered, flakes, gel, extrudate, packed or packing type etc.Therefore, the present invention also comprises the various cleaning product that can prepare or generate by described any method.They can disperse the form (by staff or machinery) of dosage to use, or can send into continuously in all suitable cleaning equipments or the e Foerderanlage and use.Cleaning product describes in detail

Each reference of this place citation is incorporated this paper by reference into.Surfactant composition by the inventive method preparation can be used in a large number in the life cleaning product composition, comprise Powdered, particulate state, gel, paste, tablet, packed, strip, the type of in two layout containers, carrying, spraying or foam shampoo and other homogeneous phase and heterogeneous life cleaning product form.They can or be used by the hand use, and/or can be consistent or indefinite variable dose use, or undertaken by automatic allocation device, or can be used in various apparatus such as washing machine or the dishwasher, or can be used for public cleaning scope of setting up such as the personal cleanliness in the public utility, can be used for wash bottle, be used for the cleaning that surgical device cleaned or be used for electronic package.Its pH scope can be very wide, as being about 2-about 12 or higher, and its storage alkali number scope also can be very wide (as being used as drain unblocking, can there be the NaOH equivalent of tens of grams in wherein per 100 gram prescriptions, washes one's hands clean-out system to slant acidity such as acidic hard surface clean-out system) from amount to the liquid medium or the low alkalinity scope of 1-10 gram NaOH.Comprise high foam and low foam detergent two types.

Various life products cleaning compositions are seen and are set forth in " Surfactant Science Series ", Marcel Dekker, and New York is in volume 1-67 and the Geng Gao volume number.Liquid composition see in detail be set forth in the volume 67 in, " Liquid Detergents ", Ed.Kuo-Yann Lai,, ISBN 0-8247-9391-9 (incorporating this paper herein by reference into) in 1997." comprising the production of washing composition of other novel material of zeolite builders ", Ed.M.Sittig, Noyes Data Corporation, (incorporating this paper herein by reference into) in 1979 are seen and be set forth in to more classical prescription (especially particulate state type).Also can be referring to Kirk Othmer ' s Encyclopedia of Chemical Technology.

Life products cleaning compositions herein unrestrictedly comprises:

Light labour type liquid washing agent (LDL): these compositions comprise that the LDL composition with the improved magnesium ion of surfactivity is (for example referring to WO 97/00930A; GB 2,292,562A; US 5,376, and 310; US 5,269, and 974; US 5,230, and 823; US 4,923, and 635; US4,681,704; US 4,316, and 824; US 4,133,779) and/or organic diamine and/or various suds-stabilizing agent and/or foam secondary accelerator such as amine oxide (for example referring to US 4,133,779) and/or tensio-active agent, softener and/or enzyme type comprise the skin feel improving agent of proteolytic enzyme; And/or antiseptic-germicide; More fully patent portfolio is seen Suractant Science Series, volume 67, the 240-248 pages or leaves.

Heavy duty detergent liquid washing agent (HDL): these compositions comprise so-called " structure " or heterogeneous (for example referring to US 4,452,717; US 4,526, and 709; US 4,530, and 780; US4,618,446; US 4,793, and 943; US 4,659, and 479; US 4,871, and 467; US 4,891, and 147; US 5,006, and 273; US 5,021, and 195; US 5,147, and 576; US 5,160,655) and two types of " non-structure " or isotropic liquids, and can be aqueous usually, also can be non-water (for example referring to EP 738,778A; WO 97/00937A; WO 97/00936A; EP 752,466A; DE 19623623A; WO 96/10073A; WO 96/10072A; US 4,647, and 393; US 4,648, and 983; US 4,655, and 954; US 4,661, and 280; EP 225,654; US 4,690, and 771; US 4,744, and 916; US 4,753, and 750; US 4,950, and 424; US5,004,556; US 5,102, and 574; WO 94/23009; And can have SYNTHETIC OPTICAL WHITNER (for example referring to US 4,470,919; US 5,250, and 212; EP 564,250; US 5,264, and 143; US5,275,753; US 5,288, and 746; WO 94/11483; EP 598,170; EP 598,973; EP 619,368; US 5,431, and 848; US 5,445, and 756) and/or enzyme (for example referring to US3,944,470; US 4,111, and 855; US 4,261, and 868; US 4,287, and 082; US 4,305, and 837; US 4,404, and 115; US 4,462, and 922; US 4,529, and 5225; US 4,537, and 706; US4,537,707; US 4,670, and 179; US 4,842, and 758; US 4,900, and 475; US 4,908, and 150; US 5,082, and 585; US 5,156, and 773; WO 92/19709; EP 583,534; EP 583,535; EP 583,536; WO 94/04542; US 5,269, and 960; EP 633,311; US 5,422, and 030; US 5,431, and 842; US 5,442, and 100) or do not have SYNTHETIC OPTICAL WHITNER and/or enzyme.Other liquid washing agent that relates to heavy duty detergent is tabulated in Surfactant Science Series, in volume 67, the 309-324 pages or leaves.

Heavy duty detergent detergent granules (HDG): these compositions comprise what is called " high-density " agglomerant or non-spray-dired and so-called " loose " or spray-dired two types.Also comprise phosphated and nonphosphateization two types.This washing composition can comprise that more common negatively charged ion-surfactant based type maybe can be so-called " height-nonionogenic tenside " type (wherein nonionogenic tenside usually remains in as in the sorbent material of zeolite or other porous, inorganic salt or on it).The production of various HDG for example is disclosed in EP753,571A; WO 96/38531A; US 5,576, and 285; US 5,573, and 697; WO 96/34082A; US 5,569, and 645; EP 739,977A; US 5,565, and 422; EP 737,739A; WO96/27655A; US 5,554, and 587; WO 96/25482A; WO 96/23048A; WO96/22352A; EP 709,449A; WO 96/09370A; US 5,496, and 487; US5,489,392 and EP 694,608A.

Tenderizer (STW): these compositions comprise various particles or liquid (for example referring to EP753,569A; US 4,140, and 641; US 4,639, and 321; US 4,751, and 008; EP 315,126; US 4,844, and 821; US 4,844, and 824; US 4,873, and 001; US 4,911, and 852; US5,017,296; EP 422,787) product of softening (softening-through-the wash) type of washing whole process, organic usually (as season) or inorganic (as clay) tenderizer.

Hard surface cleaner (HSC): these compositions comprise the clean-out system of various uses, as the liquid ceanser of paste clean-out system and various uses; The spray cleaning agent of various uses comprises glass and tile cleaner; And bleaching spray cleaner and various bathrooms clean-out system, comprise remove mould, contain SYNTHETIC OPTICAL WHITNER, disinfectant, acidity, neutrality and alkaline type.For example referring to EP 743,280A; EP 743,279A.Acidic cleaner comprises those of WO 96/34938A.

Strip soap and washing soap (BS﹠HW): these compositions comprise that the individual cleans strip soap and so-called laundry strip soap (for example referring to WO 96/35772A); Comprise the type of synthetic detergent and soap base and have the type (referring to US 5,500,137 or WO96/01889A) of tenderizer; This composition can comprise by various conventional soap manufacturing technologies such as mold pressing and/or more not conventional technology as casting, with SURFACTANT ADSORPTION to medium prepared those of porous support.(BR 9502668 also to comprise other strip soap; WO 96/04361A; WO 96/04360A; US 5,540, and 852; ).Other hand washing washing composition comprises as being set forth in GB2,292, and those among 155A and the WO 96/01306A.

Shampoo and amendment (S﹠amp; C): for example referring to WO 96/37594A; WO 96/17917A; WO 96/17590A; WO 96/17591A.Generally speaking these compositions comprise simple shampoo and what is called " two-in-one " or " having conditioning agent " two types.

Liquid soap (LS): these compositions comprise so-called " antibiotic " and conventional two types, and those have or do not have the type of skin conditioner, and comprise the type that is applicable to pump dispenser and the type of the wall-hung type device that uses by alternate manner such as public arena.

The clean-out system of special purpose (SPC): comprise that the dried cleaning system of family is (for example referring to WO96/30583A; WO 96/30472A; WO 96/30471A; US 5,547, and 476; WO96/37652A); The bleaching prefinished products that is used to do washing is (referring to EP 751,210A); The prefinished products of care fiber is (for example referring to EP 752,469A); Liquid fine-fibered types of detergents, a large amount of foamy types of especially various generations; Be used to wash the rinse aid of dish; Various liquid bleaches comprise two types of chlorine bleaching and oxygen bleachings, and sterilizing agent, mouth wash shua, artificial tooth cleaning agent are (for example referring to WO 96/19563 A; WO 96/19562A), automobile or carpet cleaner or shampoo are (for example referring to EP 751,213A; WO 96/15308A), hair rinse agent, shower gels, foam bath and individual's care clean-out system are (for example referring to 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 cleaner; With various cleaning auxiliarys as bleaching additive and " dirt adheres to " (stain-stick) or other pre-treatment type, the clean-out system that comprises special foam-type is (for example referring to EP 753,560A; EP 753,559A; EP 753,558A; EP753,557A; EP 753,556A), comprise that also anti-sunfade handles (referring to WO 96/03486A; WO 96/03481A; WO 96/03369A).

Various washing composition with lasting fragrance are (for example referring to US 5,500,154; WO96/02490) general just day by day.The method combination

The inventive method can any mode easily combines with LAB production method now or with the linear detergent alcohol method of routine.For example, the equipment of conventional assembling can all transfer the one-level OXO alcohol of producing modified alkylbenzene and/or modification to.The perhaps raw material that maybe can get (for example as from the waste liquid of LAB method or based on similar raw material source) from petrochemical complex industry according to required volume, the equipment that is used for the one-level OXO alcohol of production modified alkylbenzene of the present invention and/or modification can be used as additional (add-on) in proportion of existing LAB equipment or supporting, or installs as system separately.The inventive method can be intermittently and the successive operating method carry out.

In an additional in proportion pattern, the present invention includes preparation vinylidene alkene and adopt above-mentioned detailed various steps to prepare the alkylbenzene of modification or the one-level OXO alcohol of alkyl toluene and/or modification.With the alkylbenzene of modification or alkyl toluene with about 1: the ratio of 100-100: 1, more preferably about 1: 10-about 10: 1 (1: 5 according to appointment) is admixed to conventional linear alkyl benzene such as alkylbenzene or any DETAL of passing through of average out to C11.8 ^_In the alkylbenzene that method makes.Then adulterant is carried out sulfonation, neutralizes and is blended in the life cleaning product composition.Parallel connection technology stage or other operation stage obtain the one-level OXO alcohol of modification.

Should not limit the present invention in the scope of each details or its example (comprising each embodiment that after this is used to illustrate) in specification sheets.More in general, the present invention should comprise any life cleaning compositions that contains the tensio-active agent product (wherein the hydrophobic materials of this tensio-active agent has been used the method institute modification that the inventive method is mainly discussed) of any kind.We believe, this argumentation (especially removing linear method) can be applied in the production of for example modified alkyl sulfate and other tensio-active agent again.

Embodiment 1

By separating on the SAPO-11, dehydrogenation, on the H-mordenite, carry out alkylation, adopt sulphur trioxide/air to carry out the alkylbenzene sulfonate of sulfonation and neutralization preparation modification from the branch's hydrocarbon charging that contains of jet/diesel oil

Obtain the charging that a kind of suitable jet/diesel oil distills the cut form by kerosene.This charging contains paraffinic hydrocarbons branch and linear hydrocarbon, wherein the chain length of linear hydrocarbon be applicable to that LAB produces and wherein branch's hydrocarbon comprise methyl branched chain alkane at least about 10% and various cyclic hydrocarbon, aromatic hydrocarbon and other impurity.This logistics is continuously by (wherein the unit AC1 of Fig. 8 is mounted with as being used for the 5 dust Ca zeolites that conventional linear alkyl benzene is produced, and the unit AC2 of Fig. 8 is mounted with silicon aluminium phosphate SAPO-11 with two adsorption separation unit that are connected as shown in Fig. 1 as Fig. 8.Unit AC1 and AC2 and continuous rotary valve arrangements, raffinate tower and waste liquid tower (RC and EC) and condenser (unlabelled as shown in Figure 8 horizontal retort) with shown in other device (though being connected) in special mode mainly all be to allow and can be from its each unit (MOLEX that buys according to UOP Corp. ^_The unit) builds.To discharge from the adsorbate (extract) of Ca zeolite adsorption unit AC1, and waste liquid be sent into continuously contain among second adsorption separation unit AC2 of SAPO-11.To send into standard industry LAB method dehydrogenation unit ((PACOL_ method) is provided and is mounted with the standard LAB dehydrogenation catalyst (DeH 5_ or DeH 7_ or analogue) that belongs to UOP Corp.) as the ramose logistics that is rich in from unit AC2 of adsorbate or extract by UOP Corp..Be sent to hydrocarbon in the alkylation continuously after under the condition of various conventional preparation LAB methods, carrying out dehydrogenation, other place, this unit is conventional, difference is to be mounted with H-mordenite (ZEOCAT_FM 8/25H), carry out alkylation continuously being about under 200 ℃ the temperature therein, and finish at least about 90%, promptly the transformation efficiency of feed hydrocarbon (alkene) is at least about discharging in 90% o'clock.So obtain modified alkylbenzene.In optional variant, can repeat aforesaid method, difference is discharging when the transformation efficiency of required modified alkylbenzene reaches at least about 80% (based on alkene).By distilling the cycling stream that obtains paraffinic hydrocarbons in the rear end of alkylation and this cycling stream being sent back in the dehydrogenation reactor.Present method comprises each step and the logistics among Fig. 1 extremely herein.By other conventional distillation (this distilation steps does not have shown in Figure 1) modified alkylbenzene is purified further.Adopt sulphur trioxide intermittently or continuously the modified alkylbenzene mixture after the distillation to be carried out sulfonation (can carry out as needs) in the facility of strange land as sulphonating agent.The sulfonation details that adopts suitable air/sulfur trioxide mixture to carry out is seen among the US 3,427,342 that is set forth in Chemithon.Adopt the sodium hydroxide modified alkylbenzene sulfonic acid product of step before this that neutralizes, obtain modified alkylbenzene sulfonate sodium mixture.

Embodiment 2

By separating, adopt standard UOP method to carry out dehydrogenation on the SAPO-11, on the H-mordenite, carrying out alkylation, adopt sulphur trioxide/air to carry out the alkylbenzene sulfonate of sulfonation and neutralization preparation modification from the hydrocarbon charging of Molex_ waste liquid

From the MOLEX_ method unit of LAB equipment, particularly this equipment, obtain the suitable raw material of waste liquid or raffinate.This raffinate contains branched chain alkane and various undesirable cyclic hydrocarbon, aromatic hydrocarbon and other impurity of vast scale.This raffinate is sent to conventional configurations continuously (as according to MOLEX ^_Unitary mode) but be mounted with in the adsorption separation unit of SAPO-11.This unit is being similar to the MOLEX that is used for the production of linear alkyl benzene substantially ^_Under the used various conditions in unit and be similar to the unit AC2 described in the embodiment 1 and operate.To get rid of from the raffinate of SAPO-11 absorbing unit or waste liquid, and will according to the inventionly be rich in adsorbate that branch's logistics defines or extract and send into standard industry LAB method dehydrogenation unit continuously and (provide (PACOL by UOP Corp. ^_Method) and be mounted with belong to all standard LAB dehydrogenation catalysts (as DeH 7_) of UOP Corp.) in.It is conventional after carrying out dehydrogenation under the condition of various conventional preparation LAB methods hydrocarbon being sent to others continuously, but be mounted with in the alkylation of H-mordenite (ZEOCAT_FM 8/25H), alkylation is therein carried out continuously being about under 200 ℃ the temperature, and reaches at the transformation efficiency of alkylating reagent and to be at least about discharging in 90% o'clock.By routine distillation the modified alkylbenzene mixture is purified and with the ramose alkane circulation in dehydrogenation unit.Undertaken by shown in Figure 4 to each step herein to the method.

Adopt sulphur trioxide as sulphonating agent intermittently or continuously to the inventive method so far the place make carry out sulfonation (can in the facility of strange land, carry out) through distillatory modified alkylbenzene mixture as needs.

Adopting suitable air/sulfur trioxide mixture to carry out the sulfonated details sees among the US 3,427,342 that is set forth in Chemithon.Adopt the sodium hydroxide modified alkylbenzene sulfonic acid product of step before this that neutralizes, obtain modified alkylbenzene sulfonate sodium mixture.

Embodiment 3

By will on pyrolytic poly-(vinylidene chloride), separating, adopt standard UOP method to carry out dehydrogenation from the hydrocarbon charging of Molex_ waste liquid, on H-ZSM-12, carry out alkylation, adopting sulphur trioxide/air to carry out the alkylbenzene sulfonate of sulfonation and neutralization preparation modification

MOLEX from LAB equipment, particularly this equipment ^_Obtain the suitable raw material of raffinate form in the method unit.This raffinate contains branched chain alkane and cyclic hydrocarbon, aromatic hydrocarbon and other various undesirable impurity.This raffinate is sent into continuously in the adsorption separation unit of conventional configurations (as MOLEX ^_Type), but difference be to have introduced the LAB equipment design, claim " SARAN hereinafter ^_The unit ", be mounted with pyrolytic poly-(vinylidene chloride), sieve diameter greater than 5 dusts, disclosed Netherlands Application NL7111508 made according on October 25th, 1971.Should " SARAN unit " be similar to MOLEX ^_Operate under the unitary various condition.To discharge from the raffinate of " SARAN unit ", and make adsorbate enter standard industry LAB method dehydrogenation unit continuously (to provide (PACOL by UOP Corp. ^_Method) and be mounted with belong to all standard LAB dehydrogenation catalyst such as the DeH7_ of UOP Corp.) in.It is conventional after carrying out dehydrogenation under the condition of various conventional preparation LAB methods hydrocarbon being sent to others continuously, but be mounted with in the alkylation of H-ZSM-12, alkylation is therein carried out continuously being about under 200 ℃ the temperature, and reaches at the transformation efficiency of the hydrocarbon of input and to be at least about discharging in 90% o'clock.Prepared modified alkylbenzene mixture in step is before this distilled and adopts sulphur trioxide to carry out intermittence or sulfonation continuously as sulphonating agent.The sulfonation details that adopts suitable air/sulfur trioxide mixture to carry out is seen among the US 3,427,342 that is set forth in Chemithon.Adopt the sodium hydroxide modified alkylbenzene sulfonic acid product of step before this that neutralizes, obtain modified alkylbenzene sulfonate sodium mixture.

Embodiment 4

By separating, adopt the Pt catalyzer to carry out dehydrogenation on the SAPO-11, on acid beta-zeolite, carrying out alkylation, adopt sulphur trioxide/air to carry out the alkylbenzene sulfonate of sulfonation and neutralization preparation modification from the hydrocarbon charging of urea clathration

The raw material that from kerosene, obtains suiting by urea clathration (be used for removing the part that enrichment more has the linear hydrocarbon of industrial value).Referring to US 3,506,569.The rudimentary branch waste liquid that closes the stage from the urea cage is suitable for the hydrocarbon charging of making the inventive method.Its gas is carried to remove any activator solvent such as methyl alcohol (if exist) and to be sent to continuously with any usual manner structure (as according to MOLEX ^_The unitary mode of method) but difference be to be mounted with in the adsorption separation unit of SAPO-11.This SAPO-11 unit is being similar to standard MOLEX ^_Operate under the various conditions of processing unit.To discharge from the unitary raffinate of SAPO-11, and make adsorbate enter standard industry LAB method dehydrogenation unit continuously (to provide (PACOL by UOP Corp. ^_Method) and be mounted with non-proprietary platinum dehydrogenation catalyst) in.It is conventional after carrying out dehydrogenation under the condition of various conventional preparation LAB methods hydrocarbon being sent to others continuously, but be mounted with in the alkylation of Zeocat PB/H_, alkylation is therein carried out continuously being about under 200 ℃ the temperature, and reaches at the transformation efficiency of input hydrocarbon and to be at least about discharging in 90% o'clock.Adopt sulphur trioxide prepared modified alkylbenzene mixture in step before this to be carried out intermittence or sulfonation continuously as sulphonating agent.The sulfonation details that adopts suitable air/sulfur trioxide mixture to carry out is seen among the US 3,427,342 that is set forth in Chemithon.Adopt the sodium hydroxide modified alkylbenzene sulfonic acid product of step before this that neutralizes, obtain modified alkylbenzene sulfonate sodium mixture.

Embodiment 5

By will on the non-acid zeolite of grafting, separating, adopt DeH 9_ catalyzer to carry out dehydrogenation from the hydrocarbon charging of the kerosene cut of highly paraffinic oil, on the H-mordenite, carry out alkylation, adopting chlorsulfonic acid to carry out sulfonation and neutralization preparation modified alkylbenzene sulfonates

From low viscous crude oil such as Brent light, obtain jet/kerosene cut.It is sent to any usual manner structure continuously (as according to MOLEX ^_The unitary mode of method) but in the adsorption separation unit of different loading the (being mounted with according to US 5,326 the grafting zeolites of 928 preparations).This element is being similar to the MOLEX of conventional carrier ^_Operate under the unitary various condition.In the future unitary since then raffinate is discharged, and makes adsorbate enter standard industry LAB method dehydrogenation unit continuously (to provide (PACOL by UOP Corp. ^_Method) and be mounted with belong to all standard LAB dehydrogenation catalyst DeH9_ of UOPCorp.) in.It is conventional after carrying out dehydrogenation under the condition of various conventional preparation LAB methods hydrocarbon being sent to others continuously, but be mounted with in the alkylation of H-mordenite (ZEOCAT FM 8/25H), alkylation is therein carried out continuously being about under 200 ℃ the temperature, and reaches at the transformation efficiency of input hydrocarbon and to be at least about discharging in 90% o'clock.Adopt sulphur trioxide prepared modified alkylbenzene mixture in step before this to be carried out intermittence or sulfonation continuously as sulphonating agent.The sulfonation details that adopts suitable air/sulfur trioxide mixture to carry out is seen among the US 3,427,342 that is set forth in Chemithon.Adopt the sodium hydroxide modified alkylbenzene sulfonic acid product of step before this that neutralizes, obtain modified alkylbenzene sulfonate sodium mixture.

Embodiment 6

The cleaning product composition

10% (weight) modified alkylbenzene sulfonate sodium product of any above-mentioned exemplary method is mixed with the detergent for washing clothes particle of 90% (weight) agglomerated high density.

Embodiment 7

The cleaning product composition

In this embodiment, below abbreviation is used to represent the modified alkylbenzene sulfonates (sodium salt or potassium salt form) that makes according to any embodiment of method before this: MAS.

Below abbreviation is used to represent cleaning product additive material: C _XyThe given chain length Cxy alkyl dimethyl amine oxide of amine oxide N-oxide compound

RN (O) Me2, the average total carbon of wherein non-methyl alkyl part R

Scope is that 10+x to 10+y amylase is gone out with trade(brand)name Termamyl 60T by NOVO industry body A/S

The activity of selling is the amylolytic enzyme of 60KNU/g.Perhaps, be selected from

Following amylase: Fungamyl_; Duramyl_; BAN_ and

Be described in WO95/26397 and Novo Nordisk jointly not

The α-Dian Fenmei APA C8-C10 amido propyl group dimethylamine C of the application PCT/DK96/00056 that determines _XyAverage total carbon range of trimethyl-glycine moieties is the alkyl of 10+x to 10+y

Dimethyl betaine supercarbonate anhydrous sodium bicarbonate, size distribution is 400 μ m-1200 μ mBorax sodium tetraborate decahydrate BPP butoxy-propoxy--propyl alcohol brighteners 14,4 '-two (2-sulfo group styryl) phenylbenzene disodium brightener 24,4 '-two (4-anilino-6-morpholine also-1.3.5-triazine-2-yl) amino)

Stilbene-2,2 '-disulfonic acid disodium CaCl ₂Calcium chloride carbonate anhydrous Na ₂CO ₃, 200 μ m-900 μ m cellulosic acid cellulolytic enzymes, 1000CEVU/ gram, NOVO, Carezyme ^_The Citrate trianion citrate trisodium dihydrate, 86.4%, 425 μ m-850 μ m citric acid citric acid, anhydrous CMC Xylo-Mucine C _XyThe AS alkyl-sulphate, Na salt or other specified salt, moieties

Average total carbon range be 10+x to 10+yC _XyE _zIndustrial linear or branch's alcohol ethoxylate (does not have intermediate chain

Methyl branch), the cyclohexane of average z mole has alkyl portion

The average total carbon range that divides is 10+x to 10+yC _XyE _zS alkyl ethoxylate sulfate Na salt (or other salt), average

The oxyethane of z mole has average total carbon range of moieties

For 10+x to 10+y diamines alkyl diamine, as 1,3-propylene diamine, Dytek EP, Dytek

A (Dupont) or be selected from: dimethylamino propylamine; 1,6-oneself two

Amine; 1, the 3-propylene diamine; The 2-methyl isophthalic acid, the 5-pentamethylene diamine; 1, the 3-pentamethylene diamine;

1-methyl-diaminopropanes; 1, the 3-cyclohexanediamine; 1,2-hexamethylene two

Amine polydimethylsiloxane 40 (natural gum)/60 (fluid) (weight), the SE-76 dimethione

Natural gum (G.E Silicones Div.)/viscosity is poly-two of 350 centistokes

Blend DTPA diethylene triaminepentaacetic acid(DTPA) DTPMP diethylenetriamine five (methylene phosphonic acids) of first siloxane fluid,

Monsanto (Dequest 2060) endoglucanase endoglucanase, active 3000CEVU/ gram, NOVOEtOH alcohol fatty acid (C12/18) C12-C18 lipid acid fat acid (C12/14) C12-C14 lipid acid fat acid (C14/18) C14-C18 lipid acid fat acid (RPS) vegetable seed lipid acid fat acid (TPK) topping palm kernel fatty acid formate formate (sodium) HEDP 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid hydrotropic agent is selected from toluenesulphonic acids, naphthene sulfonic acid, isopropyl sulfonic acid, dimethylbenzene

The sodium salt of sulfonic acid, sylvite, magnesium salts, calcium salt, ammonium salt or water

Ammonium salt Isofol 12 X12 (on average) Guerbet alcohols (Condea) Isofol 16 C16 (on average) Guerbet alcohols (Condea) the LAS linear alkyl benzene sulfonate that dissolubility replaces is (as C11.8, Na or K salt) the lipase lipolytic enzyme, the 100kLU/ gram, NOVO, Lipolase ^_, perhaps

Be selected from following lipase: Amano-P:M1 lipase _;

Lipomax_; D96L-comes from as being described in the US sequence number

The natural lipase of 08/341,826 Humicola lanuginosa

The lipolytic ferment mutation; And Humicola lanuginosa bacterial strain

1: 4 toxilic acid/vinylformic acid Na salt copolymer of DSM 4106LMFAA C12-14 alkyl N-methyl glucose amide MA/AA, average weight average molecule

Amount is 70,000MBA _xE _yMiddle chain component primary alkyl ethoxylate (average total carbon number=x; Flat

Equal EO=y) MBA _xE _yS middle chain component or modification primary of (referring to embodiment 9) according to the present invention

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

Average EO=Y), MBA _yChain component primary alkyl sulphates among the S, Na salt (the MEA Monoethanolamine MEA BASF C of average total carbon number=y) _XyThe average total carbon model of MES alkyl methyl ester sulfonate (Na salt) moieties

Enclose and be 10+x to 10+yMgCl ₂The big ring manganese of magnesium chloride MnCAT bleaching catalyst (as EP 544, among the 440A) or preferably make

With [Mn (Bcyclam) Cl ₂], Bcyclam=5 wherein, 12-diformazan

Base-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane or as reference

(comparable) bridging four nitrogen heterocyclic ring NaDCC dichloroisocyanuric acid sodium NaOH sodium hydroxide C _XyNaPS alkane sulfonate (Na salt), average total carbon range of moieties

Be 10+x to 10+yNaSKS-6 formula δ-Na ₂Si ₂O ₅The two hexene triamine PB1 standard types of the quaternised ethoxylation of tetren PAEC methyl of crystalline layered silicate NaTS toluenesulfonic acid sodium salt NOBS nonanoyl hydroxy benzene sulfonate (sodium salt) LOBS C12 hydroxy benzene sulfonate (sodium salt) PAA polyacrylic acid (mw=4500) PAE ethoxylation be NaBO ₂H ₂O ₂Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER PEG polyoxyethylene glycol (mw=4600) percarbonate general formula be 2Na ₂CO ₃3H ₂O ₂SPC-D PG propylene glycol optical white seal (encapsulated) sulfonated zinc in the dextrin soluble polymer

The polymine protease protein lytic enzyme of phthalocyanine PIE ethoxylation, 4KNPU/ gram, NOVO, Savinase ^_Or

The person is selected from following proteolytic enzyme: Maxatase_; Maxacal_;

Maxapem 15_; Subtilisin BPN and BPN ';

Proteolytic enzyme B; Protease A; Proteolytic enzyme D; Primase_;

Durazym_; Opticlean_ and Optimase_ and

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

X=0-3, z=0-3, v=1-15C _XySAS secondary alkyl sulfate (sodium salt), the average carbon number scope of moieties

Be 10+x to 10+y silicate water glass, amorphous (SiO ₂: Na ₂O=2.0) polysiloxane defoamers polydimethylsiloxane Foam Control+as the silica of dispersion agent

Alkane-oxyalkylene copolymers; Foam Control: dispersion agent=10: 1-

100: 1; Perhaps pyrogenic silica and high viscosity polydimethyl

The binding substances solvent non-aqueous solvent such as the hexylene glycol of siloxanes (optional through chemical modification) also have the sulfo group benzoyl of ethylene oxide oxygen base and terephthaloyl main chain referring to propylene glycol SRP1

The terephthalate polymer STPP tripoly phosphate sodium STPP of the ethoxylation of the terephthalate polymer SRP3 methyl blocking of base end-blocking ester SRP2 sulfonated ethoxylation; anhydrous sulfate sodium sulfate; anhydrous TAED tetra acetyl ethylene diamine TFA C16-18 alkyl N-methyl glucose amide zeolite A hydrated sodium aluminosilicate, Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O; 0.1-10

The typical component that μ m zeolite MAP zeolite (maximum aluminium P) washing composition level (Crosfield) is commonly referred to " submember " can comprise spices, dyestuff, pH regulator agent etc.

Following embodiment is used to illustrate the present invention, but does not mean that restriction or define its category.Except as otherwise noted, otherwise used all umbers, percentage ratio and ratio are weight percentage.Following laundry detergent composition A-F produced according to the present invention:

	????A	????B	????C	????D	????E	????F
							MAS	????22	????16.5	????11	????1-5.5	????10-25	????5-35
Below any combination: C45 AS C45E1S LAS C26 SAS C47 NaPS C48 MES MBA16.5S MBA15.5E2S	????0	????1-5.5	????11	????16.5	????0-5	????0-10
							QAS	????0-2	????0-2	????0-2	????0-2	????0-4	????0
C23E6.5 or C45E7	????1.5	????1.5	????1.5	????1.5	????0-4	????0-4
							Zeolite A	????27.8	????0	????27.8	????27.8	????20-30	????0
Zeolite MAP	????0	????27.8	????0	????0	????0	????0
							STPP	????0	????0	????0	????0	????0	????5-65
PAA	????2.3	????2.3	????2.3	????2.3	????0-5	????0-5
							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
Proteolytic enzyme	????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 defoamers	????0.42	????0.42	????0.42	????0.42	????0-0.5	????0-1
							Vitriol, water, submember	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%
Density (grams per liter)	????400- ????700	????600- ????700	????600- ????700	????600- ????700	????600- ????700	????450- ????750

Embodiment 8

The cleaning product composition

Following liquid laundry detergent compositions A-E produced according to the present invention.Each abbreviation is with used identical in embodiment before this.

	????A	????B	????C	????D	????E
						MAS	????1-7	????7-12	????12-17	????17-22	????1-35
Below any combination: C25E1.8-2.5S MBA15.5E1.8S MBA15.5S C25 AS (linear to senior 2-alkyl) C47NaPS C26 SAS LAS C26MES	????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
						Lipid acid (TPK or C12/14)	????2	????2	????2	????2	????0-14
EtOH	????4	????4	????4	????4	????0-8
						PG	????6	????6	????6	????6	????0-10
MEA	????1	????1	????1	????1	????0-3

NaOH	????3	????3	????3	????3	????0-7
						Hydrotropic agent 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
Proteolytic enzyme	????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 defoamers	????0.12	????0.12	????0.12	????0.12	????0-0.3
Pyrogenic silica	????0.0015	????0.0015	????0.0015	????0.0015	????0-0.003
						Spices	????0.3	????0.3	????0.3	????0.3	????0-0.6
Dyestuff	????0.0013	????0.0013	????0.0013	????0.0013	????0-0.003
						Moisture/submember	Remainder	Remainder	Remainder	Remainder	Remainder
Product pH (10% go dried up solution)	????7.7	????7.7	????7.7	????7.7	????6-9.5

Embodiment 9

In the present embodiment, preparation is rich in the ramose hydrocarbon stream and it is carried out dehydrogenation, carbonylation with using one-level OXO alcohol, b-oxide and the vitriol for preparing modification.

The thick hydrocarbon charging that is fit to obtains with the form of the cut of shellfish brown coal/diesel oil or kerosene.The content of sulphur, nitrogen and aromatic substance in this charging (thinking to a certain extent has negative impact to MOLEX_ and OLEX_ adsorbent bed) is low and contain paraffinic hydrocarbons branch and linear hydrocarbon, wherein linear hydrocarbon has the chain length that is suitable for production of detergents, and wherein the ramose hydrocarbon comprises methyl ramose paraffinic hydrocarbons at least about 10%; And cyclic hydrocarbon, aromatic substance and other impurity.

Distill the two carbon cuts that thick hydrocarbon charging obtains about C14-C15.Form the suitable hydrocarbon charging that is applicable to the inventive method remainder like this.Logistics 1 referring to Figure 10.

Two adsorption separation unit that link to each other are as shown in figure 10 sent in the charging of distillatory hydrocarbon continuously, and cell S OR4/5 has loaded the 5 dust Ca zeolites and the cell S OR 5/7 that are used for conventional linear alkyl benzene preparation and has loaded silicon aluminium phosphate SAPO-11 there.The utility appliance that does not have among cell S OR 4/5 and SOR 5/7 and Figure 10 to show is that UOP Corp. permission also can be from the equipment (MOLEX_ unit) of its acquisition.What do not show has sorbent system and assists distillation and recovery tower.Be rich in the linear logistics (logistics 6 among Figure 10 from the Ca zeolite of MOLEX_ cell S OR 4/5, be rich in linear hydrocarbon) be discharged from, the second adsorption separation unit SOR 5/7 that contains SAPO-11 is sent in the ramose logistics (logistics 2 that Figure 10 is is rich in branch's hydrocarbon) that is rich in of intermediate product continuously.Be rich in the ramose logistics (logistics 3 among Figure 10 as adsorbate and extract from cell S OR 5/7, have more branch hydrocarbon) dehydrogenation unit (DEH among Figure 10) of the standard industry LAB method (PACOL_ method) that provides by UOP Corp. is provided, this equipment is equipped with by the proprietary standard dehydrogenation catalyst of UOP Corp. (DeH 5_ or DeH 7_ or analogue).Under the condition of the LAB of routine alkene feed preparation method, after part dehydrogenation (about at the most 20%), the mixture (logistics 4 among Figure 10) that is rich in branch's olefin/paraff iotan is sent into continuously DEFINE_ and the PEP_ technique unit of registering by UOP Corp..These unit hydrogenated diene impurity become monoolefine and help the content that reduces aromatic impurities.Now the olefin/paraff iotan stream (54 among Figure 10) of the purifying of gained is sent into the OLEX_ technique unit by the UOP registration, this equipment is equipped with UOP Corp. and has Patent right alkene separate sorbent.Alkene is separated back (latter is with 8 circulations of the logistics among Figure 10) from unreacted paraffinic hydrocarbons, will be rich in ramose alkene (logistics 55 among Figure 10) and send into the OXO reaction member continuously, and its operational condition is: 2-2.5: 1 H ₂: the CO ratio, pressure is about 60-90 normal atmosphere, temperature is about 170 ℃-Yue 210 ℃, and cobalt organic phosphine complex compound is housed.OXO handles and to carry out continuously, and the selectivity at modification one-level OXO alcohol is at least about 90% simultaneously, and the discharging when having reacted of the nearly all alkene in the inlet flow.Generate according to modification one-level OXO alcohol of the present invention like this.A spot of reduzate also forms paraffinic hydrocarbons.Paraffinic hydrocarbons is by steaming part from also capable of circulation to dehydrogenator.The technology of this aspect comprises step and the logistics of Figure 10.The one-level OXO alcohol of modification (logistics 57 among Figure 10) by ethoxyquin to average one mole ethylene oxide content.Perhaps ethoxyquin, third oxidation etc. can adopt the alkylene oxide of different amounts to produce required alkoxide.It can intermittently or carry out continuously, adopts oxyethane and basic catalyst (referring to Schonfeldt, Surface ActiveEthylene Oxide Adducts, Pergamon Press, N.Y., 1969) commonly used if desired in removing equipment.Now with sulphur trioxide as sulfating agent with intermittently or the successive mode handle the OXO alcohol of ethoxyquin modification (referring to " Sulphonation Technology in the Detergent Industry ", W.de Groot, Kluwer Academic Publishers, London, 1991).Thereby with in the sodium hydroxide and the product of preceding step obtain alkyl ethoxy sodium sulfate salt according to modification of the present invention.In the above in the variant of embodiment, thereby the alkyl chain length that can change hydrocarbon generates the modification OXO alcohol deutero-tensio-active agent (being used for formulation Example) of required chain length.In other variant, can carry out sulfation at OXO alcohol under the condition of the alkoxide of front to modification.

Embodiment 10

Preparation contains the indefiniteness embodiment of the on-aqueous liquid detergent for washing clothes of SYNTHETIC OPTICAL WHITNER, shown in its table composed as follows:

Table component % (weight) scope (%, weight) liquid phase LAS 25.0 18-35C24E5 or MBA14.3E5 (embodiment 9) 13.6 10-20 solvents or hexylene glycol 27.3 20-30 spices 0.4 0-1.0MBA14.4E1S (embodiment 9) 2.3 1-3.0 solid phase proteinase-10 .4 0-1.0 citrates 4.3 3-6PB1 3.4 2-7NOBS 8.0 2-12 carbonate 13.9 5-20DTPA 0.9 0-1.5 brightener 1 0.4 0-0.6 polysiloxane defoamers 0.1 0-0.3 submember surplus-

Resulting composition is anhydrous heavy labour liquid laundry detergent, and when being used for common fabric washing operation, it provides excellent dirt and greasiness removal performance.

Embodiment 11

According to following preparation liquid detergent composition.

	????A	????B	????C	????D
					MBA14.4E1S (embodiment 9)	?2	?8	?7	?5
MBA14.4S (embodiment 9)	?15	?12	?10	?8
					The C24 amine oxide	?-	?-	?-	?2
C25AS	?6	?4	?6	?8
					LMFAA	?0-5	?0-4	?0-3	?0-3
C24E5	?6	?1	?1	?1
					Lipid acid (12/18)	?11	?4	?4	?3
Citric acid	?1	?3	?3	?2
					DTPMP	?1	?1	?1	?0.5
MEA	?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
Proteolytic enzyme	?0.5	?0.5	?0.5	?0.5
					Restriction 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
					Hydrotropic agent	?-	?3	?-	?-
Isofol?12	?1	?1	?1	?1
					Polysiloxane defoamers	?0.3	?0.3	?0.3	?0.3
Water and submember	To 100%

We find that top liquid detergent composition (A-D) has very high efficient to remove various spots and dirt from fabric under various application conditions.

Embodiment 12

According to following composition of the present invention (E-J) the labour liquid laundry detergent compositions of attaching most importance to.

Embodiment #	????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
Lipid acid (C12/C14)	????7.5	????1.1	????2.0	????4.0	????5.0	????5.0
							Lipid acid (C14/C18)	????3.0	????3.5	????-	????-	????-	????-
Citric acid	????1.0	????3.5	????3.0	????3.0	????3.0	????3.0
							Proteolytic enzyme	????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
							Restriction endonuclease	????0.1	????0.1	????-	????-	????-	????-
Brightener 2	????0.1	????0.1	????-	????-	????-	????-
							Borax	????3.0	????3.0	????3.5	????3.5	????4.0	????4.0
MEA	????8.0	????4.0	????1.0	????1.5	????7.0	????7.0
							NaOH	????1.0	????4.0	????3.0	????2.5	????1.0	????1.0
PG	????12.0	????12.0	????7.5	????7.5	????7.0	????7.0
							Ethanol	????1.0	????1.0	????3.5	????3.5	????6.0	????6.0
Hydrotropic agent	????-	????-	????2.5	????2.5	????-	????-
							Submember	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus

Embodiment 13

The water base heavy labour laundry detergent composition K-O that contains medium chain branched surfactant of the present invention is listed in the table below.

Composition	?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
Lipid acid (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
						Hydrotropic agent	?3	?3	?2	?3	?0
pH=	?8.0	?8.0	?8.0	?8.0	?7.0
						Water and submember	Surplus	Surplus	Surplus	Surplus	Surplus
	?100％	?100％	?100％	?100％	?100％

Embodiment 14

According to the present invention, the waterborne liquid laundry detergent composition P-T that preparation is following:

	????P	????Q	????R	????S	????T
						MBA14.4E1S and/or MBA14.4S (embodiment 9)	????1-7	????7-12	????12-17	????17-22	????1-35
Following any combination: C25E1.8-2.5S C25AS (linear paramount 2-alkyl) C47 NaPS C26 SAS LAS C26MES	????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
						Lipid acid (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
MEA	????1	????1	????1	????1	????0-3
						NaOH	????3	????3	????3	????3	????0-7
Hydrotropic agent	????2.5	????2	????1.5	????1	????0-4
						Borax	????2.5	????2.5	????2.5	????2.5	????0-5
Proteolytic enzyme	????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 defoamers	????0.12	????0.12	????0.12	????0.12	????0-0.3
Water and accessory constituent	Surplus	Surplus	Surplus	Surplus	Surplus
						Product pH (10% deionized water solution)	????7.7	????7.7	????7.7	????7.7	????6-9.5

Embodiment 15

Preparation contains the light labour liquid dishwashing detergent compositions of modification one-level OXO alcohol deutero-tensio-active agent of the present invention:

Component	% weight A	% weight B	% weight C	% 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
					The C24 amine oxide	????4	????4	????4	????4
EO/PO segmented copolymer-Tetronic_704	????0.5	????0.5	????0.5	????0.5
					Ethanol	????6	????6	????6	????6
Hydrotropic agent (calcium xylene sulfonate)	????5	????5	????5	????5
					Mg ++(adding) with muriatic form	????3.0	????3.0	????3.0	????3.0
Water and submember	Surplus	Surplus	Surplus	Surplus
					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
The C26 trimethyl-glycine	????3	????1	???0	????2	????2	????0
							The C24 amine oxide	????0	????0	???0	????2	????5	????7
LMFAA	????3	????0	???1	????2	????0	????0
							C11E8	????0	????0	???20	????1	????0	????2
Hydrotropic agent	????0	????0	???0	????0	????0	????5
							Diamines	????1	????5	???7	????2	????2	????5
Mg ++(MgCl 2Form)	????1	????0	???0	????3	????0	????0
							Ca ++(form of calcium xylene sulfonate)	????0	????0.5	???0	????0	????0.1	????0.1
Proteolytic enzyme	????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 trianion	????0.65	????0	???0	????0.3	????0	????0
							Water and submember	To 100%

Embodiment 16

According to the present invention, the laundry detergent composition K-O that preparation is following:

	????K	????L	????M	????N	????O
						MBA14.4E0.5S (embodiment 9)	????22	????16.5	????11	????1-5.5	???10-25
Any combination of face: C45AS C45E1S LAS C26 SAS C47 NaPS C48 MES	????0	????1-5.5	????11	????16.5	???0-5
						QAS	????0-2	????0-2	????0-2	????0-2	???0-4
C23E6.5 or C45E7	????1.5	????1.5	????1.5	????1.5	???0-4
						Zeolite A	????27.8	????27.8	????27.8	????27.8	???20-30
PAA	????2.3	????2.3	????2.3	????2.3	???0-5
						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
Proteolytic enzyme	????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
Vitriol	????5.5	????5.5	????5.5	????5.5	???0-6
						Polysiloxane defoamers	????0.42	????0.42	????0.42	????0.42	???0-0.5
Water and accessory constituent	Surplus
Density (g/L)	????663	????663	????663	????663	???600- ???700

Embodiment 17

According to the present invention, the laundry detergent composition P-T that preparation is following:

	????P	????Q	????R	????S	????T
						MBA14.4E0.4S (embodiment 9)	????16.5	????12.5	????8.5	????4	???1-25
Any combination of face: C45AS C45E1S LAS C26 SAS C47 NaPS C48 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 (embodiment 9)	????5	????5	????5	????5	???0-6
Zeolite A	????15	????15	????15	????15	???10-30
						NaSKS-6	????11	????11	????11	????11	???5-15
Citrate trianion	????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
Proteolytic enzyme	????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

Vitriol	????2.3	????2.3	????2.3	????2.3	????0-25
						Polysiloxane defoamers		????0.4	????0.4	????0.4	????0-1
Water and accessory constituent	Surplus
Density (g/L)	????850	????850	????800	????850	????850

Embodiment 18

According to the present invention, the high density detergent agent prescription U-X that preparation is following:

	????U	????V	????W	????X
					Agglomerate
???????????????????????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
					Spraying
MBA14.5E5 (embodiment 9)	????5.0	????5.0	????5.0	????5.0
					Spices	????0.5	????0.5	????0.5	????0.5
Addition material
					???????????????????????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 trianion	????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
Proteolytic enzyme	????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 defoamers	????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	????-
Residuum (water/various materials)	????100	????100	????100	????100
					Density (g/l)	????850	????850	????850	????850

As explanation herein, present method can be used many different hydrocarbon chargings.The hydrocarbon charging that can be used for the conduct selection of present method comprises the mixture of particular type paraffinic hydrocarbons and/or monoene.These hydrocarbon mixtures can be selected from:

A. the mixture that meets the paraffinic hydrocarbons of following formula:

Wherein the branch's primary alkyl the total number of carbon atoms partly at this formula (comprises R, R ¹And R ²Branch) is 8-20, preferred 10-20; Be preferably about 10 to about 18; R, R ¹And R ²Independently be selected from hydrogen, C separately ₁-C ₃Alkyl and composition thereof and the very impurity such as the C of small proportion ₃-C ₇Cycloalkyl, aryl, arylalkyl and alkaryl are preferably H and C ₁-C ₃Alkyl (methyl more preferably), condition is R, R ¹And R ²Be not hydrogen and when z was 0, R or R1 were not hydrogen at least entirely; W, x, y, z independently are the integer of 0-13 separately, and restricted condition is that total carbon number upper limit and preferred w+x+y+z are 8-14.

More preferably at R, R ¹And R ²On paraffinic hydrocarbons have only hydrogen, methyl, ethyl, propyl group or butyl, be more preferably and have only hydrogen and methyl, condition is R, R ¹And R ²Comprise at least one moieties; With when having methyl, be preferably interior methyl, that is to say as much as possible to remove from 1-, the 2-of the longest denumerable chain even the position of 3-carbon.

Hydrocarbon herein also comprises:

B. monoene mixture.These monoene are relevant with top paraffinic hydrocarbons A: can be by top paraffin dehydrogenation is prepared suitable monoene.(in fact can at first isolate suitable alkene, then hydrogenation they become paraffinic hydrocarbons).Preferred alkene is monoene, although after the dehydrogenation through suitable paraffinic hydrocarbons, the alkene up to about 10% (weight) can be diolefine usually.

As paraffinic hydrocarbons, alkene herein can structurally carry out bigger variation, as possible monoene is:

Or

These structures yes schematically and not have restricted.

Hydrocarbon herein also comprises:

C. the mixture of paraffinic hydrocarbons A and alkene B

These hydrocarbon mixtures herein can be any possible array configuration exist, and can for as only contain paraffinic hydrocarbons, only contain the composition of mixture of the paraffin/olefin of alkene or arbitrary proportion.Described mixture can itself derived from coming from natural hydrocarbon such as mineral crude oil (as light crude oil or kerosene or the shellfish brown coal/diesel oil fuel that distills thus), usually these materials are carried out some processing (as closing by fractionation, selective adsorption, distillation, cage etc.) to isolate preferred hydrocarbon mixture.Perhaps, can prepare described mixture by the more complicated mixture that mixes step by step from the simple hydrocarbon of a series of compositions.Hydrocarbon mixture of the present invention can also be derived from known synthetic conversion in the petroleum chemistry, for example cracking, hydrocracking, hydroisomerization, hydrogenation, dimerisation, dehydrogenation, isomerization, disproportionation etc.In addition, suitable composition can obtain by known organic synthesis scheme (as relating to the synthetic of Grignard reaction) more hardly.Isoversion on zeolite and modified zeolite is especially favourable.

Hydrocarbon mixture herein may further include:

D. paraffinic hydrocarbons A and alkene B and other known mixture with alkene identical or more preferred different carbon number range and/or paraffinic hydrocarbons (especially linear);

Hydrocarbon herein also comprises:

The mixture of E.A-D and benzene or other araliphatic hydrocarbon.It comprises adopts other solvent such as hexanaphthene, pentane, toluene etc.

One class preferred alkane has and is selected from following formula: (II)

(III)

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

Work as a+b=10, a is the integer of 2-5, and b is the integer of 5-8;

Work as a+b=11, a is the integer of 2-5, and b is the integer of 6-9;

Work as a+b=12, a is the integer of 2-6, and b is the integer of 6-10;

Work as a+b=13, a is the integer of 2-6, and b is the integer of 7-11;

Work as a+b=14, a is the integer of 2-7, and b is the integer of 7-12;

Work as a+b=15, a is the integer of 2-7, and b is the integer of 8-13;

Work as a+b=16, a is the integer of 2-8, and b is the integer of 8-14;

Work as d+e=8, d is the integer of 2-7, and e is the integer of 1-6;

Work as d+e=9, d is the integer of 2-8, and e is the integer of 1-7;

Work as d+e=10, d is the integer of 2-9, and e is the integer of 1-8;

Work as d+e=11, d is the integer of 2-10, and e is the integer of 1-9;

Work as d+e=12, d is the integer of 2-11, and e is the integer of 1-10;

Work as d+e=13, d is the integer of 2-12, and e is the integer of 1-11;

Work as d+e=14, d is the integer of 2-13, and e is the integer of 1-12;

Compositions of hydrocarbons of the present invention can hold the impurity (as up to about 20%, preferably being lower than about 1%) of different amounts, as wherein there being the impurity of one or more ethers or pure Sauerstoffatom or interruption carbochain (so-called " oxidation " impurity); Or wherein link to each other as the impurity of side chain with carbochain as aryl, arylalkyl or alkaryl part, or wherein there is the impurity of quaternary carbon atom or diene, or the impurity that links to each other with adjacent carbons of wherein non-hydrogen partial.Of course not we are needed for these impurity.Especially preferred restriction is known that have a negative impact to biological degradation or generate malodorous impurity.In order to obtain maximum mass effect, the smaller portions of total carbon are placed on any side chain, condition is that the gained hydrocarbon preferably also has at least one carbon atom on a side chain.Preferred alkane and/or alkene can contain non-alkylbenzene aromatics, cycloalkyl and the alkyl-cycloalkyl impurity of variable quantity herein, although they more need to be removed (for example by known adsorption step).Preferred alkane and/or alkene can contain some sulphur and/or nitrogen herein, but they can generate offensive odour and owing to this or other reason, preferably by the known desulfurization of petroleum chemistry and/denitride technology removes them.

Preferred alkene is closely related with top paraffinic hydrocarbons: thus they have the structure of carrying out dehydrogenation formation in come-at-able position by any paraffinic hydrocarbons and form corresponding monoene.Especially preferred alkene is monomethyl branch and dimethyl branch, especially monomethyl ramose alkene.

Be to be understood that and recognize: describedly be used for how selecting preferred alkane and alkene to relate to following feature with the underlined notion that obtains best effect herein:

(a) accurate selection generally has the C of one or two alkyl substituent ₁₀-C ₁₈The mixture of hydrocarbon, preferably these alkyl substituents should be short as far as possible, and be positioned at least and can avoid biodegradable position.It is significantly different that hydrocarbon of the present invention thus and the utmost point are not easy biodegradable four propylidene type hydrocarbon; With

(b) preferably have at least some methyl moieties, they are not positioned at the 2-position of long hydrocarbon chain.

Do not wish to be bound by theory, we believe that the more complicated mixture in the range of definition has " modification " tensio-active agent high dissolution hardness patience, the cold water tolerance in formation and comprises that the hydrophobic materials of alkylbenzene and OXO alcohol especially has advantage.

In addition, these hydrocarbon mixtures can be widely used in the tensio-active agent of production modification.They can be used to prepare alkyl-sulphate, alkyl alkoxide, alkyl alcoxyl vitriol or the alkylaryl sulfonate such as the alkylbenzene sulfonate of modification.At first hydrocarbon mixture is converted into optional then sulfation of corresponding alcohol and/or the described alcohol of alkoxide and prepares alkyl-sulphate.Described alcohol can prepare by any usual manner such as OXO technology.Can carry out by conventional methods equally sulfation and/alkoxide.By benzene being carried out alkylation sulfonation gained alkylbenzene formation alkylbenzene sulfonate then with alkene.The alkylbenzene that forms is so-called " alkylbenzene sulfonate of modification ".

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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