CN1622990A - Alkyl toluene sulfonate detergents - Google Patents

Abstract

This invention relates to detergent compositions which employ sulfonated alkyltoluenes as surfactants, wherein the sulfonated alkyltoluenes have a higher content of the sulfonated 2-phenyl alkyltoluenes isomers than was previously available in sulfonated alkyltoluene surfactants of the prior art. Cleaning compositions according to the invention are more effective as cleaning agents over their counterparts of prior art which contain sulfonated alkyltoluenes having lower contents of the 2-phenyl alkyltoluene isomers, owing to an unexpected increase in tolerance of water hardness minerals normally associated with precipitation of the active detergent agent. Solid sulfonate salts of alkyltoluenes are also provided, including dry cleaning formulations containing same. The alkyltoluenes of this invention may be combined with alkylbenzene surfactants in order to provide detergent blends having increased water hardness tolerance, lower Krafft temperature, and increased cleaning performance over what was previously afforded by the prior art.

Description

Alkyl toluene sulfonate detergents

The application requires following right of priority: U.S. Provisional Patent Application ' 50/227,795 that on August 25th, 2000 proposed and the 01/28/00 U.S. Provisional Application No.60/178 that proposes, and 823, the two is still all unsettled at present; 09/174,891 of 10/19/98 proposition; Pending application series number 08/879,745 that proposed on June 20th, 1997, common (it is dividing an application of the series number 08/598,695 that proposed on February 8th, 1996, is United States Patent (USP) 5,770 now, 782); It and is common pending application series number: 09/616,568 of 7/14/00 proposition; 09/559,841 the part continuation application that proposed on April 26th, 2000, it is for referencial use that the content of above-mentioned all documents is all incorporated this paper into.

Background of invention

The present invention relates generally to de-sludging composition and the cleaning compositions with enhanced detergency and cleaning capacity.It relates more specifically to comprise than the de-sludging composition and the cleaning compositions of the 2-tolyl isomer of the linear alkyl tosylate of obtainable greater concn in the prior art in the past, this be because as this paper the method for having found innovation catalyzer and this class high density isomer of production is described in detail in detail.By preferred form of the present invention, as aromatic substance, its is provided the tensio-active agent that is applicable to the de-sludging goods by further alkylation and sulfonation with alkylated benzenes (for example, toluene or ethylbenzene).

Be applicable to that to remove the compound of degrease, oil, foul and other foreign matter from various surfaces and object known for some time, this compounds comprises simple soap, and they are to produce by the saponification of oil (comprising animal tallow and vegetables oil).Saponification is a kind of like this process in fact: alkali metal hydroxide aqueous solution and ester (for example, animal tallow and vegetables oil) are mixed and cause the esterification of separating of ester, generate the alkali salt of carboxylic acid (ester obtains from it), this salt is easy to be dissolved in aqueous medium usually.Importantly, the anionicsite of this class carboxylic acid alkali salt comprises the hydrophilic parts as the part of they molecular structures, that is, the carboxylate salt function, it highly attracts water molecules.Such salt also comprises the hydrophobic parts as the part of their molecular structures, it normally per molecule contain about 12～22 carbon atom hydrocarbyl portions.This class salt is called " salt of lipid acid " usually by those skilled in the art, and is called " soap " by the non-specialised staff.The aqueous solution of soap is in that to cause grease, oil and other common water-insoluble substance to become aspect solvable very effective, so, they can be by rinsing, so stay clean base material, they generally include: the object of desktop, countertop, glassware or tableware, dish, clothes, buildings, power car, human skin, people's hair etc.

Set up well though produce the industry of such soap from fat and oil, saponification chemist and other staff are continuing to seek about the material that is insoluble to the water-based medium usually being become be dissolved in improvement chemistry wherein always.For this reason, those skilled in the art have identified multiple material, and the denominator of such material is that these materials contain hydrophobic part and hydrophilic segment in their molecular structure.

The material that one class has been identified as suitable soap surrogate is linear alkyl benzene sulfonate (" a LAB sulfonate ").LAB sulfonate for example comprises a benzene ring structure usually, and it has and is connected hydrocarbyl substituent (or " alkyl substituent ") and the sulphonate-base that is in contraposition on the ring each other.Selected ring is gone up the hydrocarbon chain length of alkyl substituent and high-caliber de-sludging characteristic is provided, and simultaneously, the linearity of hydrocarbon chain has strengthened the biological degradability of LAB sulfonate.Described hydrocarbyl substituent may contain roughly 6,7,8,9,10,11,12,13,14 or 15 carbon atoms of linear array (" de-sludging scope (detergent range) ") usually, and can be connected on the phenyl ring by conventional friedel-crafts alkylation process, promptly, use corresponding alkene and utilize lewis acid catalyst (for example, aluminum chloride) and the suitable alkylating condition of this class well known by persons skilled in the art is reacted.Be applicable to that the various alkylations of producing alkylbenzene are described in the following United States Patent (USP): 3,342,888; 3,478,118; 3,631,123; 4,072,730; 4,301,316; 4,301,317; 4,467,128; 4,503,277; 4,783,567; 4,891,466; 4,962,256; 5,012,021; 5,196,574; 5,302,732; 5,344,997 and 5,574,198; And european patent application 353813 and russian patent 739,046, it is for referencial use that their full content is all incorporated this paper into.

In case as stated above alkyl is connected on the phenyl ring, just must carry out sulfonation subsequently to the linear alkyl benzene that generates, so that produce such finished product washing composition: it can be from various base materials (for example, dish, power car, crust, buildings and fabric are only lifted numerical example) dissolving grease, oil, foul etc.Sulfonation is a kind of known chemistry, and its reactant and condition are that chemical field is known to the skilled.Handle by sulfonation, cause a sulphonate-base being connected on the carbon atom in the benzene ring structure of linear alkyl benzene with chemical bond, so, except hydrophobic hydrocarbyl portion, also offer the hydrophilic sulphonate-base of this molecule on the whole.

Known, in molecular structure, introduce in the process of hydrocarbon tail base at the monoalkylation of phenyl ring, may there be several constitutional isomers, wherein, phenyl ring is connected to each point along the hydrocarbon chain of using.It is conventionally believed that, except specificity of catalyst and reaction conditions, work in the distribution of steric hindrance effect isomer in monoalkylated product of the monoolefine of application.So single phenyl ring might become 2,3,4 or 5 of the linear monoene that is connected to 10 carbon atoms, under each this class situation, produce different alkylbenzene isomer.The sulfonation of this class different substances causes a lot of different alkylbenzene sulfonates, and for different oil, grease and foul etc., they have different dissolving poweies separately.

Those skilled in the art think, the sulfonate of 2-phenylalkyl isomer is the material of being badly in need of, and has excellent cleaning and detergent power because the sulfonated products of other isomer that produces from the linear alkylbenzene washing composition of the sulfonation material of 2-phenylalkyl material preparation and alkylation process is compared.It is believed that this part be because, the separation degree of the hydrophobic and hydrophilic segment of molecule is than other isomer bigger of existence in the 2-phenyl isomer.With regard to alkylbenzene, the 2-phenylalkyl isomer product of wishing most can the following formula structure be represented:

In a preferred embodiment, n equals to be selected from 5,6,7,8,9,10,11 and 12 arbitrary integer.Because being used for producing the friedel-crafts class alkylated reaction of 2-phenylalkyl isomer of the present invention may utilize usually and be in de-sludging scope (C ₈～C ₁₅) interior alkene mixture, so, cause the distribution of various alkylbenzenes from such alkylation.

These also are fit to linear alkyl toluene of the present invention as the above-mentioned identical consideration that relates to linear alkyl benzene.Therefore, the present invention relates to the application of sulfonation 2-toluyl alkyl toluene in detergent body from alkylation of toluene (the preferred alkene with the carbon number distribution in the de-sludging scope that utilizes) in wide region.

Under the benzene alkylation situation of utilizing de-sludging scope alkene, 2-phenylalkyl benzene is a possible constitutional isomer that produces from the alkylation of benzene and alkene only, and carries out the alkylation of benzene and produce the mixture of 2-phenylalkyl benzene from the raw material (it comprises the mixture of the alkene that the de-sludging scope is interior) as reactant.This may be the cause owing to resonance stabilization, and its allows two keys effectively moving in activatory alkene/Lewis acid mixture.Usually in fact, carry out the alkylation of benzene and the set of all isomer products of producing is called " linear alkyl benzene ", perhaps " LAB ' s " usually by those of ordinary skills from the mixture that utilizes the alkene in the de-sludging scope.Usually, those skilled in the art exchange " linear alkyl benzene " or " LAB ' s " and use with their sulfonated products.When in fact people were meant sulfonation LAB ' s as washing composition, they were the LAB ' s that usually says so.These identical considerations also are fit to linear alkyl toluene, so linear alkyl toluene also can be described as " LAT ' s ".

Usually, LAB ' s industrial be to utilize classical friedel-crafts chemical reaction to produce, that is, utilize for example such catalyzer of aluminum chloride, perhaps utilize for example such strong acid catalyst of hydrogen fluoride, for example, benzene is carried out alkylation with alkene.Though these class methods cause high conversion, people know that the selectivity of the 2-phenyl isomer in the prior art in this class reaction is low, generally is about 30% or lower.LAB ' s with high percentage composition 2-phenyl isomer is required just, because when sulfonation, such compound has long " tail ", and it provides enhanced solubleness and de-sludging performance.

Though provide the alkylation of the benzene of alkylbenzene (they are provided tensio-active agent by further sulfonation) to serve many decades for industry well, the application of benzene relates to some shortcomings.For example, benzene is toxicant, needs specialized equipment for its safety operation, and its trade is to carry out under the stringent condition of each government organs' regulation.So only operation and healthy aspect just impel the chemist to seek effective alternative tensio-active agent, but they are not based on benzene.

In addition, the price of benzene is usually above other aromatic substance (can finally obtain tensio-active agent from them) that may be suitable alternatives, for example, and toluene and ethylbenzene.

Hope is its solubleness with a most important aspect of the tensio-active agent of aqueous solution form utilization.Goods need good solubleness so that work well.As previously mentioned, surfactant molecule comprises a hydrophobic part and a hydrophilic segment usually.Along with the increase (it is identical that hydrophilic group keeps) of hydrophobic group molecular weight, tensio-active agent becomes and more is insoluble in water.Equally, with regard to identical hydrophobic group, along with hydrophilic group becomes water-soluble bigger, it is more soluble in water that tensio-active agent just becomes.

The behavioral trait of tensio-active agent performance is different from those that most of other organic molecule showed.The solubleness of majority of compounds in water raises along with the temperature of water and increases.Be called as more than the certain temperature of Kraft point, the solubleness of ionogenic surfactant sharply increases.When the solubleness of ionogenic surfactant during to the temperature described point, is just obtained complicated figure.Solubleness is elevated to Krafft temperature along with temperature and slowly increases, and after this, only appropriate elevated temperature with regard to increasing suddenly of visible solubleness, and forms micella just under Krafft temperature.Below Krafft temperature, dissolve limited because do not form micella.So if the Krafft temperature of tensio-active agent is higher than the use temperature of tensio-active agent, tensio-active agent will not have enough solubleness and can not be effective as tensio-active agent under use temperature.

Therefore, provide a kind of and have enough high Krafft temperature and make the surfactant that it can use at normal temperatures, and this tensio-active agent has been represented the target of people's hopes not by benzenesulfonamide derivative.Provide that this to have higher 2-phenyl isomer content so that increase the material of its de-sludging characteristic than the obtainable material in this area will be great advance in the detergent applications.

Summary of the invention

By the present invention, linear alkyl toluenesulphonic acids salt surfactant is provided, wherein, the aromatic ring of toluene core is suspended on 2 of de-sludging scope alkyl chain.Because the ortho para guiding base that the methyl in the toluene is an aromatics to be replaced is so de-sludging scope alkene self just may be connected in the ortho position or the contraposition of this methyl.The follow-up sulfonation of the mixture of this ortho position and the linear alkyl toluene of contraposition causes the possible isomerized products of wide region, because the de-sludging scope alkyl itself on methyl on the ring and the ring all is ortho para guiding base separately.Therefore, the following isomerization structure of linear alkyl tosylate is possible:

One aspect of the present invention provides and has been used for method and the catalyzer that LAT (linear alkyl toluene) produces; this production has high substrate olefin conversion; high 2-toluyl isomer LAT production selectivity, and utilization has long lifetime and easy-to-operate catalyzer.By utilizing this aspect of the present invention, can easily produce productive rate and be higher than 70.0% and really usually above the 2-toluyl alkyl toluene of 80.0% (based on catalyst selectivity).

Importantly; the invention provides detergent composition and cleaning article with a kind of component preparation; described component comprises the mixture of sulfonated alkyl toluene; wherein; be connected alkyl on the toluene ring and may comprise the carbon atom of any amount in the de-sludging scope; in one embodiment; wherein; be connected toluyl on the alkyl at least in 70.0% (based on weight) sulfonated alkyl toluene isomer that exists and be in 2 of this alkyl; and in another embodiment; wherein, be connected phenyl on the alkyl at least in 80.0% of existence (based on weight) sulfonated alkyl toluene isomer and be in 2 of this alkyl.

The present invention further provides from a kind of tensio-active agent shape and divided detergent composition and the goods that constitute, described component comprises the mixture of following material: the first kind of alkyl toluene sulfonate component that 1) contains 2-toluyl alkyl toluene sulfonate, wherein, any percentage ratio of 40.0%～80.0% of the whole alkyl toluene sulfonate isomer that exist in the described first kind of alkyl toluene sulfonate component of 2-toluyl alkyl toluene sulfonate isomer comprises, described content comprises one of each percentage between two numerical value percentage ratio; And 2) second kind of surface active agent composition, it may comprise: a) alkylbenzene sulfonate, wherein, phenyl ring is connected on the linear alkyl at least 60% of whole alkylbenzene sulfonate isomer that the isomer comprises of the position except that this alkyl 2 exists; B) alkylbenzene sulfonate, wherein, phenyl ring is connected on the linear alkyl at least 70% of whole alkylbenzene sulfonate isomer that the isomer comprises of the position except that this alkyl 2 exists; Perhaps c) branched-alkyl benzene sulfonate, or its combination; Perhaps d) alkyl toluene sulfonate, wherein, the toluene ring is connected on the linear alkyl at least 60% of whole alkyl toluene sulfonate isomer that the isomer comprises of the position except that this alkyl 2 exists; E) alkyl toluene sulfonate, wherein, the toluene ring is connected on the linear alkyl at least 70% of whole alkyl toluene sulfonate isomer that the isomer comprises of the position except that this alkyl 2 exists; Perhaps f) branched-alkyl tosylate, or its combination.

Can the branched-alkyl tosylate be introduced the product of the present invention's preparation by one of following two kinds of methods.At first, available branched olefin replaces a part to be used for the linear olefin feedstock that the toluene cycloalkylation is reacted, thus the alkyl toluene mixture that provides a kind of sulfonation to use, and wherein, alkyl toluene comprises a selected amount of branched-alkyl thing.Second kind provides the method for branched-alkyl tosylate to be in end article of the present invention, in finished product of the present invention is produced branched-alkyl toluene is used as blending compound.So, by fusion in alkylation reaction product or branched substances is provided, might in end article of the present invention, provide the branched-alkyl tosylate of wide region amount; Yet preferably, branched isomer accounts for 50.0% any amount of being less than of whole alkyl toluene sulfonate isomer of existing in the given goods of the present invention.In another preferred form of the present invention, branched isomer accounts for 15.00% any amount of being less than of whole alkyl toluene sulfonate isomer of existing in the given goods of the present invention.In another preferred form of the present invention, branched isomer accounts for 2.00% any amount of being less than of whole alkyl toluene sulfonate isomer of existing in the given goods of the present invention.

In preferred form of the present invention, in second kind of surface active agent composition, there is (described content comprises one of each percentage between two numerical value percentage ratio) the more low activity isomer (isomer except that 2-phenyl isomer) of linear alkyl benzene or linear alkyl toluene with any amount based on second kind of surface active agent composition gross weight 0.00%～70.00%.

In preferred form of the present invention, second kind of surface active agent composition may comprise alkyl toluene sulfonate or alkylbenzene sulfonate, wherein, phenyl ring is connected on the linear alkyl at least 50% of whole alkylbenzene sulfonate isomer that the isomer comprises of the position except that this alkyl 2 exists.

In another preferred form of the present invention, second kind of surface active agent composition may comprise alkyl toluene sulfonate or alkylbenzene sulfonate, wherein, phenyl ring is connected on the linear alkyl at least 40% of whole alkylbenzene sulfonate isomer that the isomer comprises of the position except that this alkyl 2 exists.

In another preferred form of the present invention, second kind of alkylbenzene sulfonate component may comprise alkyl toluene sulfonate or alkylbenzene sulfonate, wherein, phenyl ring is connected on the linear alkyl at least 30% of whole alkylbenzene sulfonate isomer that the isomer comprises of the position except that this alkyl 2 exists.

So, may contain sulfonation 2-phenylalkyl toluene by the alkylbenzene sulfonate component of another embodiment of the present invention, its amount is 30.00wt% at least based on sulfonated alkyl toluene component gross weight.In another form of the present invention, the alkyl toluene sulfonate component may contain sulfonation 2-phenylalkyl toluene, and its amount is 40.00wt% at least based on sulfonation phenylalkyl toluene component gross weight.In another form of the present invention, the alkyl toluene sulfonate component may contain sulfonation 2-phenylalkyl toluene, and its amount is 50.00wt% at least based on sulfonated alkyl toluene component gross weight.In another form of the present invention, the alkyl toluene sulfonate component may contain sulfonation 2-phenylalkyl toluene, and its amount is 60.00wt% at least based on sulfonated alkyl toluene component gross weight.In another form of the present invention, the alkyl toluene sulfonate component may contain sulfonation 2-phenylalkyl toluene, and its amount is 70.00wt% at least based on sulfonation phenylalkyl toluene component gross weight.In another form of the present invention, the alkyl toluene sulfonate component may contain sulfonation 2-phenylalkyl benzene, and its amount is 80.00wt% at least based on sulfonated alkyl toluene component gross weight.

By with the conventional mixture fusion of the linear alkylbenzene washing composition of sulfonation, can use that material production provided by the invention is a kind of to be suitable for the mixture component make the de-sludging goods, sulfonated alkylbenzene and sulfonated alkyl toluene, any desired content of the gross weight that accounts for 2-phenylalkyl benzene or 2-phenylalkyl toluene isomer or its combination that it has is in 18.00%～82.00% scope, and described content comprises one of each percentage between two numerical value percentage ratio.The suitable washing composition of wide range of application (described in hereinafter embodiment) use and the component of cleaning compositions of being formulated in of the mixture of such sulfonated alkylbenzene and sulfonated alkyl toluene.

Also found, catalyzer of the present invention can with existing aluminum chloride or hydrogen fluoride alkylation catalyst and with and LAB or LAT be provided, its 2-phenyl or 2-toluyl content of isomer are higher than the plant produced of application conventional catalyst.So, can improve existing facility to comprise one or more reactors that fill fluorine-containing mordenite of the present invention.Like this, the slip-stream of reactant can be sent to mordenite, returns conventional alkylation system and be guided from the effusive material of mordenite.This embodiment has several advantages.For example, it is minimum that investment cost is reduced to, because conventional equipment is just suitable.Also have, the factory of innovation can be by its operator higher 2-phenyl isomer LAB or the LAT of autonomous production as required.That is to say that factory needn't produce absolute high-load 2-phenyl isomer LAB or LAT, but can arbitrarily produce high-load 2-phenyl isomer.In one embodiment, extract the slip-stream of reactant out, deliver to one or more reactors that fill fluorine-containing mordenite catalyst.Just can merge and the more high-content 2-phenyl isomer LAB that recently exists in the product of HF or aluminium reaction device or the product of LAT be provided from the effluent of fluorine-containing mordenite reactor with effluent from HF or aluminium reaction device.

Invention relates to cleaning article at one aspect wide, these goods can be used to clean various surfaces or base material, and they have strengthened the patience of the water hardness, wherein, described goods comprise a kind of alkyl toluene sulfonate component, it has much higher 2-phenyl isomer content than commercially available goods in the past, also contains known other component that is applicable to preparation soap, washing composition etc., comprises conventional linear alkyl benzene sulfonate washing composition.

The present invention relates to a kind of method that is applicable to the manufacture order alkyl toluene at another aspect wide, and it comprises: in the presence of fluorine-containing mordenite, under the condition that forms linear monoalkyl toluene, toluene is contacted with the alkene that contains about 8～about 30 carbon atoms.

The present invention relates to a kind of method of producing linear alkyl toluene at another aspect wide, and it comprises: toluene is contacted in the presence of fluorine-containing mordenite with the alkene with about 8～about 30 carbon atoms and form first kind of linear alkyl toluene stream; B) toluene is contacted with the alkene with about 8～about 30 carbon atoms in the presence of conventional linear alkyl benzene alkylation catalyzer and form second kind of linear alkyl toluene stream; And c) merge first kind of linear alkyl toluene stream and second kind of linear alkyl toluene stream and form the third linear alkyl toluene stream, and the single sulfonated products for preparing from this method.

The present invention relates to a kind of method of producing linear alkyl toluene that is applicable to aspect wide at another, and it comprises: merge from the product of conventional linear alkyl benzene alkylation reaction device with from the product of linear alkyl alkylation of toluene reactor (filling fluorine-containing mordenite).

The present invention relates to a kind of method of producing linear alkyl toluene at another aspect wide, and it comprises: a) the paraffin dehydrogenation is generated alkene; B) by pipeline the primary raw materials stream of toluene and alkene is delivered to conventional linear alkyl benzene alkylation reaction device; C) primary raw materials stream in the conventional linear alkyl benzene alkylation reaction device is contacted with conventional linear alkyl benzene alkylation catalyzer under the condition of the reaction of carrying out toluene and alkene effectively and generate first kind of linear alkyl toluene products; D) extract a part of primary raw materials stream out and this part is contacted under the condition of the reaction of carrying out toluene and alkene effectively with fluorine-containing mordenite and generate second kind of linear alkyl toluene products from pipeline; E) merge first kind and second kind of linear alkyl toluene products and form thick line shape alkyl toluene and flow; And f) distillation thick line shape alkyl toluene flows and separates unreacted toluene in first distillation column, forms the linear alkyl toluene stream of no toluene.

This method can be chosen wantonly and comprise the following steps: g) the linear alkyl toluene of the no toluene of distillation flows and separates any alkene in second distillation column, thus form linear alkyl toluene stream; And h) alkyl toluene of second kind of no alkene of distillation flows and the overhead product of linear alkyl toluene product of purifying and the bottom stream that discharge contains any heavier substances is provided in the 3rd distillation column.

The present invention relates to a kind of method that is applicable to the manufacture order alkyl toluene at another aspect wide, it comprises: will comprise and have about 8～alkene of about 30 carbon atoms and the raw material of toluene imports fluorine-containing mordenite catalyst bed under the condition of manufacture order alkyl toluene, make toluene, alkene and monoalkyl toluene fall into (falling into) reboiler from catalyst bed, discharge monoalkyl toluene from reboiler, and the inclusion in the heating reboiler and refluxing toluene is further contacted with fluorine-containing mordenite.

The present invention relates to the alkylating mordenite that is applicable to toluene and alkene at another aspect wide, and it has about 10: 1～about 100: 1 silicon-dioxide ratio aluminum oxide mol ratio; Wherein, handle mordenite and make this mordenite contain the fluorine of about 0.1wt%～about 4wt% with aqueous hydrogen fluoride solution.

The present invention relates to a kind of chemical mixture at another aspect wide; it comprises and utilizes the method that this paper enlightens and/or the linear alkyl toluene of Catalyst Production; described chemical mixture is applicable to the mixture of the linear alkyl toluene of production sulfonation, and this mixture contains than the higher sulfonation 2-toluyl alkyl toluene concentration of product of utilizing art methods and catalyzer to obtain in the past.

The present invention is included as goods that the final user provides and the industrial powerful composition that is applicable to following aspect aspect wide at another: all purpose cleaner, pine tar microemulsion, liquid dishwashing soap, based on the powdery and the liquid laundry agent of enzyme, do not contain the powdery scouring agent of enzyme etc., because found, than the effect and the cleaning action that can have the more application of the sulfonation LAT mixture of high-content 2-phenyl isomer from the product that the enlightenment of prior art obtains so far, improve all cleaning compositions that contain conventional sulfonated alkylbenzene washing composition (no matter they are linear or branching).No matter be with the linear alkyl benzene sulfonate in whole replacements of linear alkyl tosylate of the present invention or the part replacement prior art goods, above-mentioned all is correct, wherein, the material that linear alkyl tosylate beguine of the present invention obtains according to prior art has higher 2-phenylalkyl concentration (any percentage ratio of 30.00%～80.00% comprises one of each percentage between two numerical value percentage ratio).

The present invention relates to a kind of method that is applicable to the fluorine-containing mordenite of preparation aspect wide at another, it comprises, make to have about 10: 1～mordenite of silicon-dioxide ratio aluminum oxide mol ratio in about 100: 1 scopes contacts with the aqueous hydrogen fluoride solution of hydrogen fluoride concentration in about 0.1wt%～about 10wt% scope, so produced fluorine-containing mordenite, collect this fluorine-containing mordenite, subsequent drying by filtering.

The mordenite catalyst that above-mentioned fluorine is handled advantageously produces the highly selective to 2-phenyl isomer in the preparation of LAB and LAT, produce about 70% or bigger selectivity usually.Moreover the mordenite life-span that fluorine is handled is long, and preferred active the reduction has only 25% or littler after 400 hours aborning.Technology by Fig. 1 and 2 shown device operation has this advantage, that is, thereby the toluene that rises from reboiler ceaselessly cleaning catalyst prolong life of catalyst.In addition, the present invention advantageously produces only a spot of dialkyl group toluene (it is not particularly suitable for washing composition production), and only a spot of 1,2,3,4-tetralin derivative.

The present invention provides the solid salt of alkyl toluene sulfonate in yet another aspect, and this solid salt may contain the required various positively charged ions of charge balance.

The present invention comprises the finished product detergent composition that is applicable to clean textile, dish, crust and other base material in yet another aspect, said composition is made of following component: a) alkyl toluene sulfonate surface active agent composition, its amount is 0.25wt%～99.50wt% based on finished product detergent composition gross weight, described component is characterised in that, it comprises the water-soluble sulfonate based on the 2-phenyl isomer of the alkyl toluene of being represented by following general formula of any amount of the 26.00wt%～82.00wt% of this component gross weight:

Wherein, the arbitrary integer that n equals 4～16, wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be sulphonate-base, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be the substituting group that is selected from methyl and ethyl, described content comprises one of each percentage between two numerical value percentage ratio; And b) the known preparation soap that is applicable to of 0.50%～99.75% any amount, other component of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, ether sulfate, alkylphenol ethoxylate, fatty acid amide, alhpa olefin sulfonate, paraffin sulfonate, betaine, sequestrant, the tallow amine ethoxylate, polyetheramine ethoxylate, ethylene oxide/propylene oxide segmented copolymer, fatty alcohol ethylene epoxide/propylene oxide low-foaming surfactant, methyl ester sulfonate, alkyl polysaccharide, N-methyl glucose amide, alkylation sulfonation phenyl ether, and the 2-phenyl isomer content is less than 26.00% water-soluble alkylbenzene sulfonate or alkyl toluene sulfonate.

Mordenite catalyst of the present invention is suitable for the catalyzer of making to produce by the present invention the method production LAT of LAT.LAT is suitable for the raw material of doing production sulfonation LAT (it self is suitable for and makes tensio-active agent).

Some term and phrase that this paper uses have following meanings:

The milliequivalent of the titratable acid of " Meq/g " every gram catalyzer of expression, it is a unit that is used to describe catalyst acidity.Acidity promptly, adds excessive alkali (for example, sodium hydroxide), then this catalyzer of back titration usually by measuring with alkalimetric titration in catalyzer.

" Conv. " and " transformation efficiency " expression is converted into the molecular fraction of the given reactant of product.Usually, in enforcement of the present invention, olefin conversion about 95% or more.

The molecular fraction of specific components in " Sel. " and " selectivity " expression product.Usually, in enforcement of the present invention, be about 70% or bigger to the selectivity of 2-phenyl isomer.

" de-sludging scope " expression comprises the molecular species of an alkyl, and each institute's carbon atom quantity of described alkyl is: 8,9,10,11,12,13,14 or 15, and comprise LAB, LAB sulfonate, LAT, LAT sulfonate and monoolefine.

When hydrocarbon chain that relates to a part that belongs to alkylbenzene or alkyl toluene (no matter whether this alkylbenzene or alkyl toluene are sulfonated) or alkyl chain, " roughly linear " expression contains 7～16 carbon atoms, be connected to each other and form the hydrocarbon of straight chain, wherein, may only connect hydrogen atom or a methyl side groups on the carbon atom of described straight chain.

When hydrocarbon chain that relates to a part that belongs to alkylbenzene or alkyl toluene (no matter whether this alkylbenzene or alkyl toluene are sulfonated) or alkyl chain, " branched-alkyl " expression contains 4～16 carbon atoms, be connected to each other and form the hydrocarbon of straight chain, wherein, may have a hydrogen atom and any alkyl that be connected with them as side group, except that methyl (including but not limited to ethyl, propyl group and butyl) on one or more carbon atoms of described straight chain.

" branched-alkyl benzene " expression contains a molecular species that is connected the branched alkyl chain on the phenyl ring.

" branched-alkyl toluene " expression contains a molecular species that is connected the branched alkyl chain on the toluene molecule loop section, no matter the relative position of the methyl of toluene and branched alkyl chain how.

The water-soluble salt of the branched-alkyl benzene that " branched-alkyl benzene sulfonate " expression is sulfonated.

The water-soluble salt of the branched-alkyl toluene that is sulfonated of " branched-alkyl tosylate " expression is no matter with respect to the isomery position of methyl how sulphonate-base and alkyl.

The phenyl ring that has connected at least one alkyl on " 2-phenylalkyl benzene " representative ring, wherein, described alkyl comprises 7～16 (comprising each integer between them) and is connected to each other and forms the roughly any amount carbon atom of linear chain, and wherein, phenyl ring roughly connects this alkyl in the adjacent carbon atom place of terminal carbon of linear chain at this.Has another alkyl that is connected with it in a methyl and the 2-phenylalkyl benzene like this, with on the carbon atom that phenyl ring is connected.

A kind of toluene molecule of " 2-phenylalkyl toluene " expression, except its methyl, it also has another connected alkyl at least, wherein, this another alkyl comprises 7～16 (comprising each integer between them) and is connected to each other and forms the roughly any amount carbon atom of linear chain, and wherein, the loop section of toluene molecule roughly connects this alkyl in the adjacent carbon atom place of terminal carbon of linear alkyl chain at this.Has another alkyl that is connected with it in a methyl and the 2-phenylalkyl toluene like this, with on the carbon atom that the toluene ring is connected.2-phenylalkyl toluene and 2-tolyl alkylbenzene are synonyms.

A kind of toluene molecule of " 2-tolyl alkylbenzene " expression, except its methyl, it also has another connected alkyl at least, wherein, this another alkyl comprises 7～16 (comprising each integer between them) and is connected to each other and forms the roughly any amount carbon atom of linear chain, and wherein, the loop section of toluene molecule roughly connects this alkyl in the adjacent carbon atom place of terminal carbon of linear alkyl chain at this.Has another alkyl that is connected with it in a methyl and the 2-phenylalkyl toluene like this, with on the carbon atom that the toluene ring is connected.

" sulfonation 2-phenylalkyl benzene " expression 2-phenylalkyl benzene defined above, it further comprises one and is connected as the sulphonate-base on the phenyl ring of above-mentioned 2-phenylalkyl benzene, no matter with respect to the position of alkyl position how this sulphonate-base on the ring; Yet the most common and preferably, sulphonate-base is connected on the phenyl ring contraposition with respect to alkyl.

" sulfonation 2-phenylalkyl toluene " expression 2-phenylalkyl toluene defined above, it further comprises one and is connected as the sulphonate-base on the aromatic ring of above-mentioned 2-phenylalkyl toluene, no matter this sulphonate-base, methyl and alkyl position each other is how; Yet most preferably, sulphonate-base is connected on the phenyl ring contraposition with respect to alkyl.

The mixture of " LAB " expression linear alkyl benzene, it comprises a phenyl ring that is connected with any carbon atom of the interior roughly linear alkyl chain of de-sludging scope.

The mixture of " LAT " expression linear alkyl toluene, it comprises the toluene molecule that any carbon atom of the roughly linear alkyl chain that its aromatic ring and de-sludging scope are interior is connected.

" LAB sulfonate " expression LAB, it is comprised an acid sulphonate-base that is connected with phenyl ring (thereby forming parent acid) by further sulfonation, subsequently, by forming the aqueous solution more easily more molten than this parent acid with following any material neutralization, that is, and alkali metal hydroxide, alkaline earth metal hydroxides, ammonium hydroxide, alkyl ammonium hydroxide, the perhaps known any chemical agent that generates the water soluble linear alkylbenzene sulfonate with the reaction of linear alkyl Phenylsulfonic acid of those skilled in the art.

" LAT sulfonate " expression LAT, it is comprised an acid sulphonate-base that is connected with the aromatic ring of this LAT (thereby forming parent acid) by further sulfonation, subsequently, by forming the aqueous solution more easily more molten than this parent acid with following any material neutralization, that is, and alkali metal hydroxide, alkaline earth metal hydroxides, ammonium hydroxide, alkyl ammonium hydroxide, the perhaps known any chemical agent that generates the water soluble linear alkylbenzene sulfonate with the reaction of linear alkyl Phenylsulfonic acid of those skilled in the art.

The LAB or the LAT sulfonate of " 2-phenyl isomer " expression 2-phenylalkyl benzene that context guaranteed.

A kind of like this compound of " sulfonated aromatic alkylide " expression, it comprises: a phenyl ring, connected a sulphonate-base on the carbon atom of ring structure, also have at least one in the de-sludging scope, be connected the alkyl on the ring structure carbon atom; So LAT and LAB material belong to this class.

Unless otherwise indicated, all percentage ratios that provide in this specification sheets and the appended claims thereof are all represented with weight percentage.

The accompanying drawing summary

Fig. 1 shows and is used to implement first successive reaction distillation column synoptic diagram of the present invention;

Fig. 2 shows and is used to implement second successive reaction distillation column synoptic diagram of the present invention;

Fig. 3 is the representative processes synoptic diagram of one embodiment of the invention, show one and the conventional LAB alkylation reactor of fluorine-containing mordenite reactor bonded of the present invention (it also is applicable to and produces LAT), wherein, the slip-stream that flows to the popular response device is sent to the mordenite reactor, and wherein, can regulate from the fluid of the high 2-phenyl isomer LAB of mordenite reactor or LAT (deciding as the case may be) and change the content of 2-phenyl isomer LAB in the effluent of conventional LAB alkylation reactor or LAT;

Fig. 4 is another representative processes synoptic diagram of one embodiment of the invention, show and first conventional LAB alkylation reactor of fluorine-containing mordenite reactor bonded of the present invention (it also is applicable to LAT production), wherein, the slip-stream that flows to the popular response device is sent to one or two in a pair of mordenite reactor, and wherein, send into second conventional LAB alkylation reactor after the effluent of the LAT of first LAB alkylation reactor or LAB effluent and one or two mordenite reactor merged;

Fig. 5 shows the washing composition that utilizes the alkylbenzene with different 2-phenyl isomer content data in graph form is studied in total de-sludging that the cloth sheet carries out;

Fig. 6 shows the turbidity of solution in the different hardness aqueous solution that contains conventional alkylbenzene tensio-active agent;

Fig. 7 shows and contains the alkylbenzene tensio-active agent turbidity of solution in the different hardness aqueous solution of (its 2-phenyl isomer content is about 80%);

Fig. 8 shows the turbidity that has the aqueous solution of constant water hardness in the presence of different mixtures, the linear alkyl benzene sulfonate and the linear alkyl tosylate of each self-contained different amount of described mixture, wherein, the 2-phenyl isomer content in alkylbenzene sulfonate and the alkyl toluene sulfonate based on the whole sulfonate gross weights that exist greater than 80wt%.

                Detailed description of the present invention

The catalyst that is used for preparing linear alkyl toluene of the present invention is fluorine-containing modenite. Modenite is a class zeolite. Catalyst of the present invention is from the h-mordenite with about 10: 1～about 100: 1 silica-alumina mol ratio (generally have 0.1% or still less sodium) preparation. More particularly, the raw material thread geolyte has about 10: 1～about 50: 1 silica/alumina mole ratio. Process commercially available original h-mordenite with hydrogen fluoride (" the HF ") aqueous solution, produce active, life-span catalyst of the present invention long and high selectivity. In such HF processing procedure, and in the roasting process of the modenite that follow-up described HF-processed, silica/alumina mole ratio increases usually. Finished catalyst of the present invention shows as the fluorine content of about 0.1wt%～about 4wt% (more normal about 1%).

The aqueous solution that is used for processing modenite may contain the HF concentration of certain limit. Usually, the minimum about 0.1wt% of HF concentration. Be lower than this Cmin, the effect that fluorine is processed greatly reduces, and causes the needs of undesirable reprocessing. In general, the HF upper limit of concentration is about 10wt% or less. When being higher than the concentration of about 10wt%, HF concentration is difficult to too greatly prevent that HF from destroying the crystalline structure of modenite, so detrimentally affect it as the efficient of the catalyst of LAB and LAT production.

The HF aqueous solution can be prepared by diluting commercially available 48%HF solution to desired concn. Also the HF bubbling can be passed in the water and the HF aqueous solution is provided.

Usually, modenite powder or ball process by adding in the HF aqueous solution under stir under about 0 ℃～about 50 ℃ temperature. Continue to stir and contact to a period of time that is enough to reach required fluorine content in the modenite. This time may become with following factors, and for example, HF concentration is with respect to the HF amount of solution of the modenite amount of processing, the mixing speed of application, and temperature. After the processing, can pass through the filtered and recycled modenite, then dry. Can also be with given HF solution impregnation modenite to initial humidity, and process modenite with hydrogen fluoride gas. Preferably, the modenite that the described Fluoridizing of roasting is crossed in air should be used for before the alkylating. Preferred sintering temperature should be in about 400 ℃～about 600 ℃ scope. Except hydrofluoric acid and hydrogen fluoride, alternative modenite fluorization agent comprises ammonium fluoride, fluorinated silicon compound and fluorohydrocarbon.

The modenite that HF-of the present invention processes generally has based on about 0.1 wt% of modenite gross weight or more fluorine. Usually, above-mentioned fluorine-containing modenite comprises about 4wt% or fluorine still less. The most normal fluorine that contains about 1wt% of this fluorine-containing modenite.

Described modenite can be used as powder, is the ball form, is used for implementing the present invention as particle or as extrudate. Can use adhesive well known to those skilled in the art (for example, aluminium oxide, silica or its mixture) modenite is processed into ball or extrudate.

Be used for the reactant that LAT produces

In enforcement of the present invention, with alkene alkylation of toluene is generated LAT. The such processing and these reactants of purifying that can usually carry out by those of ordinary skills. In this respect, preferably, reactant is not moisture and pure. Have about 8～about 30 carbon atoms at the alkene of implementing to use when of the present invention, preferred about 10～about 14 carbon atoms, for example, alkene commercially available or that produce as the dehydrogenation paraffin raw material. Preferably, described alkene is monounsaturated. Most preferably, described alkene is the alhpa olefin that contains terminal alkene unit.

The alkene that contains 10～14 carbon number weight ranges can utilize method known to those skilled in the art from C usually₁₀～C ₁₄The dehydrogenation of mineral wax mixture obtains. Such paraffin dehydrogenation provides two keys monoene mixture on end carbon place and its adjacent carbon atom in chain, also more remaining unconverted paraffin. So, loaded C₁₀～C ₁₄The effluent of the dehydrogenation reactor of mixture comprises a kind of mixture usually, and it mainly contains paraffin, and has about 5～20% olefin(e) centent, and obtains easily. Usually, the olefin(e) centent of described alkene-mineral wax mixture may be 8～10wt%.

Can utilize the successive reaction distillation column of describing among Fig. 1 to carry out operation of the present invention and produce the 2-phenyl isomers of the LAT with chemical formula that preamble provides. In Fig. 1, the raw mix of toluene and alkene (usually with about 1: 1～100: 1 toluene than alkene molar ratio range) flows to feed(raw material)inlet 14 from feedstock pump 10 via pipeline 12. Raw mix is fallen the mordenite catalyst bed 32 of filling, and alkylated reaction occurs in this existence that is in fluorine-containing modenite. Alternatively, although in Fig. 1, do not depict, toluene and alkene can be imported respectively described bed and in bed, mix, perhaps can be on reactant being imported before the catalyst bed by line the blender mixed reactant, perhaps reactant can be injected respectively described bed top, utilize the standard filler of bed top to mix, perhaps reactant can be sprayed into the reative cell of bed top. The laboratory scale catalyst bed 32 of describing among Fig. 1 all is that 1.1 inches pipe consists of by two sections internal diameters, and their length is 9.5 inches and 22 inches. In catalyst bed 32, the raw mix of whereabouts also contacts with the unreacted toluene vapor (it is heated to backflow by heater 40 in reboiler 42) that rises. The steam of this rising is by thermocouple 38, latter's monitor temperature and provide feedback to heater 40. The toluene and/or the alkene steam that rise also pass standard filler 36 (for example, 7.5 inches Goodloe packings). Thermocouple 30 heating of the steam that rises to being connected to bottom temp controller 28, when temperature drops to when being lower than the setting level, temperature controller activates heater 40.

Beginning before the operation, availablely entering and the nitrogen purge and wash system of the pipeline 58 of flowing through via pipeline 54. Begin after the operation, above system, keep the nitrogen cover layer. Also have begin before the operation with the nitrogen purge during, may wish heatable catalyst bed 32 in order to from fluorine-containing modenite, drive away moisture.

Be collected in the water trap 24 after (with benzene vapour) liquefaction in condenser 21 from raw mix or the residual moisture that enters system. If raw material very dry (not moisture) just needn't be used water trap 24. Cause the catalyst life more grown except anhydrating. So water trap 24 is chosen wantonly. The same Fig. 2 that is fit to. Condenser 21 is to utilize cooling medium (water that for example, enters condenser 21 and flow out via mouth 20 via entrance 22) cooling. If necessary, can be by opening the water in the bleed valve 26 discharging water traps 24.

If necessary, when the LAT content in the reboiler 42 is elevated to desired level, can remove bottom LAT product from system via pipeline 47, utilize gravity or bottom pump 48 to extract product out. If extract like this product out, with regard to open valve 44.

In Fig. 1, utilize dip-tube 46 (it is chosen wantonly) to increase a little pressure in the reboiler 42, thereby with the elevation of boiling point of benzene once or twice. Equally, can choose the pressure that utilizes pressure generator 56 to come elevation system wantonly. Can use other normal pressure aggrandizement apparatus. So the pressure in can the increase system causes the elevation of boiling point of toluene to about 200 ℃.

In Fig. 1, drawn the controlling mechanism of hot shut off valve 50 and pump shut off valve 52, if the liquid level in the system is raised to such level, they just close heat and pump. These controlling mechanisms are chosen wantonly, and can comprise that they so that catalyst bed do not contact with the bottom of reboiler. Pipeline 60 is connected to pump shut off valve 52 top of condenser 21 in the system.

When implementing alkylation of toluene of the present invention, can utilize various operating conditions. In this respect, the temperature of catalyst bed may be with reactant, the speed that imports catalyst bed, this variations such as size. In general, according to pressure catalyst bed is maintained the reflux temperature of toluene. Usually, the temperature of catalyst bed is higher than about 100 ℃, and the most suitable about 110 ℃～130 ℃ or higher in order to keep rational reaction rate, and about 250 ℃ or lower in order to avoid reactant and product degradation also avoid catalyst because of coke accumulation inactivation. Preferably, temperature is in about 120 ℃～about 200 ℃ of scopes. During contact procedure, can under each pressure, operate this technique, the atmospheric approximately pressure of the most normal application. When utilizing the operating procedure of system shown in Fig. 1 and 2, reboiler temperature is remained on the temperature of toluene and alkene evaporation, this temperature becomes with alkene, for the alkene of 10～14 carbon atoms, normally about 110 ℃～about 300 ℃ of temperature. The component of reboiler will become in time, is about 5: 1 but usually be set at first toluene than the ratio of alkene, keeps this ratio in implementation process of the present invention. The speed that raw material imports catalyst bed is variable, and liquids in general hourly space velocity (" LHSV ") is about 0.05hr^-1～about 10hr^-1, more normal is about 0.05hr^-1～about 1hr^-1 The toluene that imports catalyst bed was than alkene mol ratio normally about 1: 1～about 100: 1. In the industrial toluene alkylation operation, generally under about 2: 1～about 20: 1 mol ratio, operate, it is also applicable to enforcement of the present invention, and with described alkene as the alkene that contains 5%～20% alkene-paraffin hydrocarbon mixture charging. Described alkene-paraffin hydrocarbon mixture is produced by the dehydrogenation on noble metal catalyst of corresponding paraffin raw material industrial usually.

Described another successive reaction distilling apparatus among Fig. 2. In Fig. 2, raw mix enters reactor via charging aperture 114. Raw mix falls and to enter catalyst bed 132 by post, there alkylation occurs and generates LAT. The temperature of the described catalyst bed 132 of thermometer sleeve 133 monitorings. Catalyst bed 132 can be chosen wantonly externally to be heated and is contained in the 1-1/4 inch stainless steel sleeve pipe. Filled Goodloe packing in the filled column 136 and 137. LAT product and unreacted toluene and alkene fall to entering reboiler 142 by filled column 136. In reboiler 142, the inclusion in the electric heater 140 heating reboilers 142 so that the vapours of toluene and alkene rise to from reboiler 142 and arrive at least catalyst bed 132. If necessary, can be by opening bottom valve 144 from reboiler 142 discharging bottom LAB products (after flowing through pipeline 147 and filter 145, discharging). Can be in condenser 121 the condensation raw mix residual water or enter the residual water of system, condenser 121 is what to utilize via the cooling medium cooling of outlet 122 and inlet tube 120. Condensed water falls into water trap 124, and it can open bleed valve 126 dischargings as required. Utilize the temperature in thermocouple 138,130 and 165 monitoring systems. This system comprises pressure relief valve 166. Import nitrogen and above system, keep the nitrogen cover layer via inlet duct 154. When the fluid level in the reboiler was elevated to level control actuator 150, level control actuator 150 was just actuated bottom level control valve 151 and is opened. Pipeline 160 is controlled the top that actuator 150 is connected to condenser 121 in the system with level.

Although single catalyst bed system has been shown in the system of describing among Fig. 1 and Fig. 2, should understand that the multi-catalyst bed bioreactor belongs to scope of the present invention, also have a plurality of feed(raw material)inlets, water trap, product line road etc. In addition, this technique can operate by intermittent mode, perhaps by the continued operation that utilizes piston flow design, trickle bed design and design of Fluidized bed.

Think along with the increase of alkene mean molecule quantity (particularly when carbon atom average surpasses 14), selective and may sharply increase to the conversion ratio of the LAT LAT of 2-isomers (particularly about). The alkylate that the modenite that utilizes HF to process can be carried out if necessary, is delivered to second, post-processing catalyst bed with the improvement productive rate. This operation is chosen wantonly, and is considered to depend on end user's needs and wish. An example of this second catalyst is the clay that HF processes, and for example, contains the imvite of about 0.5% fluoride. This catalyst also can work to reduce the bromine number of alkylate to being lower than about 0.1 (depending on condition).

Use modenite of the present invention when conventional LAT alkylation is combined

The variable 2-phenyl isomer content of product

Fluorine-containing modenite of the present invention is produced the LAT with high 2-phenyl isomer content usually, for example, is higher than about 70%. At present, the LAT buyer who produces washing agent would rather use the LAT of 2-phenyl isomer content in about 30～about 40% scope, but is not reaching on the market this content. Conventional LAT alkylation techniques can not realize these higher 2-phenyl isomer content. HF, it is to be used at present the most widely used catalyst at industrial-scale production LAT, causes in the product stream of reactor about 16～18% 2-phenyl isomers. By contrast, aluminium chloride produces about 26～28% 2-phenyl isomers. The inventor recognizes, needs a kind of method, and it produces the 2-phenyl isomers product of required scope.

Have now found that, modenite of the present invention and conventional LAB alkylation catalyst (for example, HF and aluminium chloride alkylation catalyst) combination can be used. This can be sent to by extraction the reactant slip-stream of conventional LAB reactor, again with this slip-stream guide wire geolyte reactor and influenced. Because the product of conventional LAB Catalyst Production ratio is from the much lower 2-phenyl isomer content of having of modenite production of the present invention, merging causes a kind of product from the LAT product of each catalyst, and it has recently from the higher 2-phenyl isomer content of the product of conventional LAB alkylation catalyst. For example, although the 2-phenyl isomer content that catalyst of the present invention produces usually is 70 % or larger, HF method commonly used produces about 16～18% 2-phenyl isomers. By merging the effluent from each catalyst to fixed-ratio, the mixture that forms will have required any 2-phenyl isomer content, in the scope of this content between the 2-phenyl isomer content HF catalyst prod and the mordenite catalyst product. So, the amount of reactant that can be by delivering to mordenite catalyst is regulated the 2-phenyl isomer content and/or by storing from the 2-phenyl isomer products of mordenite catalyst for mixing with product from conventional LAB alkylation catalyst subsequently, so the 2-phenyl isomer content of any desired level in the realization finished product. An advantage of the present invention relates to the ability of improving existing conventional LAB system with the reactor that fills the modenite that fluorine of the present invention processed. This can make increase their existing equipment and do not interrupt their production of the existing user of conventional LAB technology, and this provides huge expense advantage for the producer.

The most conventional LAB catalyst of normal use is HF alkylation reactor and aluminium chloride alkylation catalyst. Other alkylation catalyst comprises: various zeolites, alumina silica, various clay and other catalyst.

Fig. 3 has drawn one and has implemented representativeness of the present invention, non-restrictive version, wherein, the modenite of fluorine being processed is combined with the HF alkylation reactor and LAT with high 2-phenyl isomer content (with respect to the product of only producing from the HF reactor) is provided. The LAT alkylation implication that the schematic diagram of Fig. 3 shows is based on the raw material from paraffin dehydrogenation equipment. Before the present invention, the factory that draws among Fig. 3 should carry out without modenite reactor 220 routine operation.

So, in routine operation, fresh paraffin being fed to conventional dehydrogenation unit 210 via pipeline 211, the paraffin of recirculation imports from paraffin post 250 via pipeline 252. Then, be pumped to via pipeline 214 from the dehydrogenation paraffin of dehydrogenation unit 210 and fill conventional LAB catalyst (for example, HF) conventional alkylation reactor 230. The paraffin raw material of dehydrogenation can be provided from any supplier certainly. The source of dehydrogenation paraffin (alkene) is not critical for implementing the present invention. LAT product from alkylation reactor 230 can pass through a series of destilling tower purifying subsequently.

In this respect, by pipeline 231 thing is flowed out in alkylation and be transported to toluene post 240. Should understand, alkylate can be sent from Workplace and purifying. In addition, the concrete purification scheme of application is not critical for implementing the present invention, but, and the representative of the just conduct industrial operation commonly used shown in Fig. 3. In Fig. 3, from thick LAT product, distill out unreacted toluene. Then toluene is recycled to alkylation reactor 230. The thick product of LAT that does not contain toluene from toluene post 240 is pumped via pipeline 241 arrival paraffin posts 250, distills out the paraffin of any existence here, and the paraffin that steams is recycled to paraffin dehydrogenation unit 210 through pipeline 252. The thick LAT alkylates that does not contain paraffin from paraffin post 250 is transported to refining post 260, steams the LAT of purifying here and passes through pipeline 262 discharges. Extract heavy component (for example, dialkyl group compound and alkene derivatives) via pipeline 261 out from refining post 260.

Implementing when of the present invention, utilizing the reactor 220 and the conventional alkylation reactor 230 that fill the modenite that fluorine processed to make up. In the embodiment of the present invention of describing in Fig. 3, from the slip-stream of pipeline 214 derivation toluene/dehydrogenation paraffin raw materials, pumping realizes the production of high-load 2-phenyl isomers here by modenite reactor 220. Then, come the LAT product of the high-load 2-phenyl isomers of autoreactor 220 to be guided Returning pipe 214 through pipeline 222. Also can be directly to modenite reactor 220 charging toluene and dehydrogenation paraffin (alkene), rather than by the slip-stream from pipeline 221. In addition, the effluent of reactor 220 (if there is no unreacted alkene) also can be delivered directly to toluene post 240, merges for follow-up and conventional alkylation reactor 230 products, and perhaps input pipe 231, and it is to toluene post 240 feed. Should understand that post 240,250 and 260 can remain on condition well known to those skilled in the art (for example, pressure and temperature), if necessary, also can be filled conventional material.

Fig. 4 has described an alternative design drawing shown in Fig. 3. In Fig. 4, with compound modenite bed 320,321 and conventional alkylation reactor 330,340 applied in any combination. Can make easily the operation of one of them modenite reactor, and another reactor down-time allows catalyst regeneration. For example, in operation, via pipeline 301 supply olefin feedstocks (dehydrogenation paraffin), and via pipeline 302 supply toluene or other aromatic raw materials. Reactant after the fusion can flow to standard alkylation reactor 330 after pipeline 304b is flowing through heat exchanger 303. Can extract a part through pipeline 304a and mix logistics supply modenite reactor. The degree that mixed feedstream is extracted can become according to the content of required 2-phenyl isomers in the finished product. In another embodiment, can be fed to first alkylation reactor 330 (if particularly in operation not with second alkylation reactor 34) from the reactor 320 that fills modenite, 321 product.

The slip-stream reactant is delivered to dewater unit 317 after optionally utilizing pump 306 pumpings by heat exchanger 305. In dewater unit 317, in dehydrating tower 310, steam the water in the reactant. The steam that rises through pipeline 311a out and flow through heat exchanger 312 (carrying out condensation inside). Come the effluent of automatic heat-exchanger 312 to enter water trap 318 through pipeline 311b. Via the water that pipeline 313 is discharged in the water trap 318, the organic layer of bottom is by the anti-dehydrating tower 310 of delivering to. Reactant after the dehydration can be discharged through pipeline 316 and is transported to pipeline 316a or 316b again. Can extract by conduit 314b the reactant of some dehydrations out, send over-heat-exchanger 315 to return tower 310 by pipeline 314a. In this respect, heat exchanger 315 can play reboiler.

After the reaction, the LAT product is transferred by entering pipeline 322 and 331 behind the heat exchanger 323 from pipeline 322a or 322b in reactor 320 or 321. If necessary, one of Regenrable catalyzed dose of bed, for example, by utilizing regenerative heater 350 roastings, heater 350 can be by being connected to selected reactor by valve system and the hardware that does not illustrate shown in the dotted line 351. Reactor 320 and 321 can be chosen simultaneously operation wantonly. Reactor 320 and 321 can load the mordenite catalyst of the apparent arbitrary form of those skilled in the art. Usually, adopt piston flow to arrange. The catalytic amount of using can become according to various Considerations (for example, the classification of reactant and flow velocity, temperature and other variable). Merging effluent from popular response device 330 and modenite reactor 320 or 321 can be fed to second popular response device 340, perhaps if there is no unreacted alkene, just can choose wantonly and directly deliver to purifying workshop section (effect of popular response device is to finish the reaction of any alkene that does not transform in modenite reactor 320,321). In Fig. 4, enter purifying workshop section from the effluent of second conventional alkylation reactor. Second alkylation reactor can be used to react autoreactor 330,320 and 321 unreacting material, thereby reduces the recirculation load.

Should understand that various designs all are desired, and these figure should not seen and be restricted the present invention or claim. For example, can use other reactor and miscellaneous equipment.

Following embodiment has set forth the present invention, but does not want they are regarded as the scope of restriction the present invention or claim.Unless otherwise indicated, all percentage ratio is all based on weight.In an embodiment, all reactant all be technical grade and use by the raw material of receiving.The device of describing among Fig. 1 is used for embodiment 2～4.The device of describing among Fig. 1 is used for embodiment 5.

Though the embodiment of this paper relates to and carries out the alkylation of benzene by the present invention and the LAB of the 2-phenyl isomer content with increase is provided, but can utilize toluene to replace benzene as raw material, adopt aforementioned temperature of producing, provide LAT with identical catalyzer and equipment about LAT.

Should note, embodiment 2 has set forth, the mordenite catalyst that utilizes the fluorochemical of Embodiment B to handle, produce LAB from the paraffin dehydrogenation, realized good catalyst life (250+hrs) and do not had regenerated catalyst, kept 2-phenyl isomer selectivity＞70% and high LAB productive rate simultaneously but do not have the loss of significant fluorochemical.On the other hand, comparative example 1 utilizes untreated mordenite (not adding fluorochemical) to show LAB output sharply to reduce.In addition, embodiment 3 and 4 has set forth, and utilizes the benzene/C of 5: 1 mol ratios ₁₀～C ₁₄The mordenite catalyst that the fluorochemical of olefin feedstock mixture and Embodiment B was handled is at 0.2～0.4hr ^-1LAB when the Different L HSV ' s in the scope operates down produces.Catalyst life may be above 500 hours.Embodiment 5 has set forth the LAB that the mordenite catalyst handled with fluorochemical carries out and has produced, and at this moment, carries out alkylation at higher temperature with under pressure.Embodiment 6～8 has set forth the performance of the mordenite catalyst that three kinds of HF with different fluorochemical load handled.Embodiment 9 shows, and in fact observe with highly fluorinated mordenite does not have alkylation activity.

Embodiment A

This embodiment has set forth the preparation of the mordenite of hydrogen fluoride modification.

At room temperature, toward 30g acidifying mordenite (LZM-8, SiO ₂/ Al ₂O ₃Than being 17; Na ₂Owt%0.02, surface-area 517m ²/ g, powder is from Union Carbide Corp.) middle 600ml 0.4% hydrofluoric acid solution that adds.After 5 hours,, use distilled water wash, 120 ℃ of following dry nights, 538 ℃ of following roastings by the solids removed by filtration zeolite.

Embodiment B

This embodiment has set forth the preparation of the mordenite of hydrogen fluoride modification.

The mordenite of past 500g acidifying, dealuminzation is (from the CBV-20A of PQ Corp., SiO ₂/ Al ₂O ₃Mol ratio is 20; Na ₂O 0.02wt%; Surface-area 550m ²/ g, 1/16 " diameter extrudate is 538 ℃ of one nights of following roasting) in add the solution of 33ml 48%HF in 1633ml distilled water, cooling mixture in ice stirs a night on rotary evaporator, then the solid extruded of filtered and recycled.Further wash extrudate with distilled water, 100 ℃ of following vacuum-dryings, subsequently 538 ℃ of one nights of following roasting.

The mordenite analytical results of handling shows:

F:1.2% acidity: 0.49meq/g

Embodiment 1

This embodiment has set forth, and utilizes the mordenite catalyst of hydrogen fluoride modification to prepare linear alkyl benzene.

The mordenite that adds 100ml benzene (SILVER REAGENT) in the flask of condenser and Dean Rodney Stark couch water trap and add the modification of 10g hydrogen fluoride (the method preparation by embodiment A) is housed toward 500ml.Mixture is refluxed 15～20 minutes to remove small amount of moisture, then the benzene (50ml) that merges is added 1-dodecylene (10g) and inject above-mentioned flask, solution was refluxed 3 hours.

During cooling, by removing by filter the mordenite catalyst of modification, flash distillation filtrate is to remove unreacted benzene, subsequently by the gc analysis bottom liquid.

The canonical analysis data are summarized in the table 1.

Dodecylene CONV. (%)	LAB isomeric distribution (%) 2-Ph 3-Ph 4-Ph 5-Ph 6-Ph					Heavy component (%)	Linear LAB (LLAB) (%)
								99.7	79.9	?16.6	?0.8	?1.3	?1.3	?0.2	?95.9

Table 1

Embodiment 2

This embodiment has set forth, and the mordenite catalyst that utilizes hydrogen fluoride trealment to cross prepares linear alkyl benzene from dehydrogenation paraffin.

In embodiment 2, with containing about 8.5%C ₁₀～C ₁₄The C of alkene ₁₀～C ₁₄Dehydrogenation paraffin sample is with benzene alkylation.Alkylation is to carry out in the operating unit shown in Fig. 1.

Carry out alkylation by following method: at first, in reboiler, load 5000ml benzene/dehydrogenation mineral wax mixture (10: 1 mol ratios, benzene/C ₁₀～C ₁₄Alkene), the mordenite of the Embodiment B of again 250cc HF being handled " the internal diameter reaction zone of packing 1.1 into.With Goodloe packing mordenite is remained on original position.Then, the reboiler liquid heat to refluxing, is added C with the speed of 100cc/hr with benzene ₁₀～C ₁₄Dehydrogenation mineral wax mixture (10: 1 mol ratios, benzene/C ₁₀～C ₁₄Alkene) top of catalyzer post in the gatherer continuously.(LHSV＝0.4hr ^-1)。

Under stable state, reflux conditions, extract liquid product continuously out from reboiler, and from water trap drainage water continuously.By the thick liquid product of vapor-phase chromatography periodic analysis.Reboiler temperature is usually in 97～122 ℃ span of control.Column cap temperature variability is 78～83 ℃.The analytical results of concluding is found in the table 2.

After experiencing 253 hours aborning, the mordenite catalyst that the HF that reclaims by analysis revealed handled: F:1.1%; Acidity: 0.29meq/g; H ₂O:0.3%

Time on the wire (Hrs)	Sample	Alkylide concentration (%)	2-phenyl selectivity (%)	C 6H 6Concentration (%)
					0	?0	?1.4		?32.3
2	?1	?3.4		?19.7
					4	?2	?5.8	?74.9	?16.6
6	?3	?6.6	?75.8	?25.2
					32	?4	?7.9	?80.7	?27.0
56	?5	?7.8	?82.7	?27.0

Time on the wire (Hrs)	Sample	Alkylide concentration (%)	2-phenyl selectivity (%)	C 6H 6Concentration (%)
					69	?6	?7.3	?81.4	?27.4
94	?7	?6.5	?82.0	?27.8
					118	?8	?6.0	?78.4	?27.7
142	?9	?5.9	?81.3	?26.9
					166	?10	?5.4	?81.5	?27.3
207	?11	?5.3	?81.3	?26.1
					229	?12	?5.1	?81.1	?27.4
253	?13	?4.9	?81.4	?28.1

Table 2

The comparative example 1

This embodiment has set forth, and utilizes untreated mordenite catalyst, prepares linear alkyl benzene from dehydrogenation paraffin.Press the working method of embodiment 9, mordenite (the initial mordenite of Embodiment B) untreated with 250cc, roasting loads alkyl plant, and liquid starting material comprises benzene and adds C ₁₀～C ₁₄Dehydrogenation mineral wax mixture (benzene/the C that is 10: 1 mol ratios ₁₀～C ₁₄Alkene).

Representative result is summarized in the table 3.

Mordenite by the analysis revealed recovery: acidity: 0.29meq/g; H ₂O:2.1%

Time on the wire (Hrs)	Sample	Alkylide concentration (%)	2-phenyl selectivity (%)	C 6H 6Concentration (%)
					0	?0			?11.2
2	?1	?6.50		?9.9
					4	?2	?7.16	?73.2	?17.1
6	?3	?7.09	?73.1	?26.4
					22	?4	?8.61	?73.9	?26.6
31	?5	?10.49	?67.4	?15.8
					46	?6	?7.39	?75.0	?27.7
70	?7	?6.39	?75.1	?28.5
					93	?8	?6.08	?73.6	?23.0
144	?9	?5.21	?73.6	?15.8
					157	?10	?4.40	?73.9	?26.2
180	?11	?3.06	?69.6	?27.1
					204	?12	?1.32		?19.5
228	?13	?1.32		?33.3

Table 3

Embodiment 3

This embodiment has also set forth, and the mordenite catalyst that utilizes hydrogen fluoride trealment to cross prepares linear alkyl benzene from dehydrogenation paraffin.

Press the operation steps of embodiment 2, the mordenite filling alkyl plant that the HF of usefulness 250cc Embodiment B handled, liquid starting material comprises benzene and adds C ₁₀～C ₁₄Dehydrogenation mineral wax mixture (benzene/the C that is 5: 1 mol ratios ₁₀～C ₁₄Alkene), generally in 122～188 ℃ scope, the column cap temperature is 78～83 ℃ to reboiler temperature.Representative analytical results is summarized in the table 4.

After experiencing 503 hours aborning, the mordenite catalyst that the HF that analysis revealed reclaims handled: F:1.0%; Acidity: 0.35meq/g; H ₂O:0.1%

Time on the wire (Hrs)	Sample	Alkylide concentration (%)	2-phenyl selectivity (%)	C 6H 6Concentration (%)	The a alkylide concentration (%) of calibration
						0	?0	?1.0		?8.9	?1.1
2	?1	?3.5	?61.8	?0.3	?3.5
						4	?2	?7.1	?72.1	?0	?7.1
6	?3	?6.8	?76.7	?7.2	?7.3
						34	?4	?8.4	?79.7	?14.3	?9.8
71	?5	?7.2	?81.8	?14.6	?8.5
						96	?6	?6.5	?80.8	?15.5	?7.7
119	?7	?6.3	?80.6	?15.1	?7.4
						643	?8	?6.0	?81.0	?14.3	?7.0
168	?9	?5.9	?80.7	?14.4	?6.9
						239	?10	?5.0	?78.2	?8.8	?5.5
263	?11	?5.3	?79.2	?13.5	?6.2
						288	?12	?5.0	?79.6	?16.5	?6.0
311	?13	?5.4	?79.4	?4.1	?5.6
						335	?14	?5.5	?79.2	?8.2	?6.0
408	?15	?4.9	?79.4	?13.1	?5.6
						432	?16	?4.7	?78.8	?14.4	?5.5
456	?17	?4.4	?78.5	?14.1	?5.1
						479	?18 a	?4.7	?78.6	?2.7 b	?4.8
488	?19 b	?4.9	?78.5	?2.4 c	?5.0
						503	?20 b	?5.1	?78.9	?0.6 c	?5.1

Table 4

^aCalibrate for the benzene in the effluent sample

^bApplied pressure 8 " H ₂O

^cApplied pressure 12 " H ₂O

Embodiment 4

This embodiment has also set forth, and the mordenite catalyst that utilizes hydrogen fluoride trealment to cross prepares linear alkyl benzene from dehydrogenation paraffin.

Press the operation steps of embodiment 2, in having the complete glassware device of catalyzer post, reboiler, condenser and control member shown in Fig. 1, carried out alkylation.The mordenite that the HF of filling 500cc Embodiment B handled in the reaction zone.Liquid starting material comprises benzene and adds C ₁₀～C ₁₄Dehydrogenation mineral wax mixture (benzene/the C that is 5: 1 mol ratios ₁₀～C ₁₄Alkene).Feed rate is 100cc/hr (LHSV:0.2hr ^-1).

Under stable state commonly used, reflux conditions, the reboiler temperature scope is in 131～205 ℃, and the column cap temperature is 76～83 ℃, and representative result is summarized in the table 5.

Pressure (inch H 2O)	Reboiler temperature (℃)	Line duration (Hrs)	Sample	Alkylide concentration (%)	2-phenyl selectivity (%)	??C 6H 6Concentration (%)	Calibration aAlkylide concentration (%)
								??12	??205	??2	??1	??8.2	??74.3	??0.5	??8.3
	??193	??4	??2	??9.2	??75.0	??0.4	??9.2
									??175	??6	??3	??10.0	??74.8	??2.3	??10.3
	??204	??21	??4	??12.7	??78.7	??0.3	??12.7
									??146	??44	??5	??11.7	??81.0	??10.4	??12.9
	??136	??68	??6	??11.5	??81.8	??10.0	??12.7
										2-3 days	??C b	??11.6	??81.4	??9.4	??12.7
	??136	??93	??7	??11.3	??82.6	??10.8	??12.5
										4-5 days	??C-1 b	??11.0	??81.8	??11.0	??12.2
	??142	??165	??8	??10.4	??83.0	??11.4	??11.5
									??142	??189	??9	??10.2	??83.4	??10.5	??11.2
	??146	??213	??10	??9.7	??80.2	??11.2	??10.7
									??139	??238	??11	??9.6	??83.4	??11.1	??10.7
	??143	??261	??12	??9.9	??81.9	??11.0	??11.0
									??133	??333	??13	??9.2	??83.4	??11.3	??10.3
	??138	??356	??14	??8.9	??83.5	??11.1	??9.9
									??138	??381	??15	??8.8	??83.0	??11.3	??9.8
	??131	??405	??16	??8.7	??82.8	??11.2	??9.7

Table 5

^aCalibrate about the benzene in the effluent sample

^bComposite prod

Embodiment 5

This embodiment has set forth, and the mordenite catalyst that utilizes hydrogen fluoride trealment to cross prepares linear alkyl benzene from dehydrogenation paraffin.

Press the operation steps of embodiment 2, utilize the complete stainless steel device that has catalyzer post, reboiler, condenser and control member shown in Fig. 2 to carry out benzene and C ₁₀～C ₁₄The alkylation of dehydrogenation paraffin.The mordenite that the HF of the about 250cc Embodiment B of filling handled in the post.Liquid starting material comprises benzene and adds C ₁₀～C ₁₄Dehydrogenation mineral wax mixture (benzene/the C that is 10: 1 mol ratios ₁₀～C ₁₄Alkene).LHSV changes to 0.4hr from 0.2 ^-1

In the scope of column temperature and reboiler temperature He in the top hole pressure scope, carry out alkylation.Representative result is summarized in the table 6.

Column temperature (℃)	Pressure DIFF outlet (psi) (psi)		The still temperature (℃)	Time (hr)	Sample (#)	Alkylide concentration (%)	2-phenyl selectivity (%)	C 6H 6Concentration (%)
									149-129	?0.1	?0	?188	?4	?1	?3.8		?6.3
152-126	?0	?0	?200	?20	?2	?1.8		?32.7
									195-108	?0	?0	?199	?25	?3	?5.7		?8.7
218-111	?0	?0	?201	?28	?4	?0.8		?67.5
									212-118	?0	?0	?201	?44	?5	?8.8	?71.7	?4.5
209-114	?0.2	?0	?198	?52	?6	?2.4		?47.3
									228-116	?0	?0	?197	?68	?7	?6.9	?72.6	?12.4
187-107	?0.5	?0	?197	?76	?8	?2.9	?74.6	?44.1
													?76	?9 a	?4.8	?72.9	?25.3
					?9C b	?6.8	?72.2	?1.0
									174-107	?0	?0	?178	?6	?10	?4.1	?79.2	?54.9
170-106	?0	?0	?172	?22	?11	?2.0		?59.8
													?28	?12 a	?6.6	?76.8	?26.8
142-107	?0	?0	?136	?31	?13	?4.8	?67.9	?18.9
									141-110	?0	?0	?138	?47	?14	?4.4	?65.9	?16.9
142-110	?0	?0	?136	?55	?15	?5.0	?63.9	?16.6
									168-111	?0	?0	?131	?71	?16	?4.1	?64.8	?16.7
170-108	?0	?0	?150	?79	?17	?5.0	?72.0	?8.8
									175-113	?0	?0	?143	?95	?18	?5.9	?68.1	?15.2
145-106	?0	?5.2	?188	?14	?19	?3.2	?60.2	?9.0
									149-108	?0	?4.2	?186	?20	?20	?4.8	?66.3	?12.0
160-118	?0	?11.7	?213	?29	?21	?4.2		?6.7
									160-119	?0	?9.3	?210	?44	?22	?5.2		?6.6

Table 6

^aComposite prod

^bStripped composite prod

Embodiment 6～8

These embodiment have set forth, and utilize mordenite catalyst (having different fluorochemical processing horizontals) the preparation linear alkyl benzene of hydrogen fluoride modification.

Press the operation steps of embodiment 1, in alkyl plant, load benzene (100ml), 10g hydrogen fluoride modified mordenite sample, add the mixture of benzene (50ml) and 1-decene (10g) by the method preparation of Embodiment B.Tested three kinds of mordenites that HF handled with following composition:

Contain 0.25%HF on catalyzer " C " mordenite (CBV-20A)

Contain 0.50%HF on catalyzer " D " mordenite (CBV-20A)

Contain 1.0%HF on catalyzer " E " mordenite (CBV-20A)

In each test, the sample that regularly extracts bottoms liquid fraction carries out gc analysis.The result is summarized in the table 7.

Catalyzer	Time	??％LLAB	?％ISOS	％HVY	??％2Ph	??％3Ph	??％4Ph	??％5Ph	％6&7Ph
										??D	??10	??11.75	??0.14	??0	??73.36	??21.87	??2.89	??0.94	??1.02
	??20	??12.43	??0.21	??0	??72.97	??21.96	??3.14	??1.13	??0.81
											??30	??12.88	??0.21	??0	??72.67	??22.13	??3.03	??1.16	??1.01
	??40	??12.27	??0.22	??0	??73.02	??21.92	??2.85	??1.06	??1.14
											??50	??12.15	??0.98	??0	??72.46	??21.67	??3.21	??1.17	??1.49
	??50	??12.24	??1.01	??0	??72.53	??21.63	??3.23	??1.12	??1.44
											??60	??12.28	??0.21	??0	??72.96	??22.07	??2.93	??1.14	??0.91
	??60	??11.98	??0.21	??0	??72.97	??22.21	??2.93	??1.17	??0.83
??C	??10	??12.2	??0.18	??0	??72.54	??22.46	??3.21	??0.98	??0.82
											??20	??12.7	??0.39	??0	??71.51	??22.61	??2.91	??1.02	??2.13
	??30	??12.52	??0.21	??0	??71.96	??22.68	??2.96	??1.04	??1.36
											??40	??12.75	??0.21	??0	??71.84	??22.67	??3.22	??1.02	??1.25
	??50	??12.98	??0.21	??0	??71.57	??22.81	??3.16	??1.08	??1.39
											??60	??12.54	??0.21	??0	??71.45	??22.81	??3.19	??1.12	??1.44
	??60	??12.33	??0.21	??0	??71.61	??22.87	??2.92	??1.05	??1.31
??E	??10	??10.56	??0.05	??0	??75.19	??19.41	??2.18	??3.22
											??20	??12.95	??0.15	??0	??74.36	??19.23	??3.01	??3.4
	??30	??13.44	??0.18	??0	??74.11	??19.42	??3.2	??3.27
											??40	??13.16	??0.15	??0	??074.16	??19.38	??3.12	??3.34
	??50	??13.1	??0.15	??0	??74.43	??19.16	??3.21	??3.28
											??60	??12.83	??0.15	??0	??74.28	??19.49	??2.88	??3.35
	??60	??12.87	??0.16	??0	??73.82	??19.97	??2.8	??3.2

Table 7

Embodiment 9

This embodiment has set forth the inertness of the hydrogen fluoride modified mordenite of a large amount of loads.

Press the operation steps of embodiment 2, in alkyl plant, loaded the mordenite (CBV-20A) that 100cc crosses by the hydrogen fluoride trealment of the method preparation of Embodiment B, but had more the HF of high loading (content of fluoride 4.8%).The acidity of the mordenite that described HF handled is 0.15meq/g.

The alkylate that does not have significant quantity by gas chromatography determination.

Embodiment 10

The preparation of high 2-position isomer C12-alkyl toluene

Use mordenite, CBV20A (a kind of Zeolyst that derives from, Inc.ofConshohocken, the mordenite catalyst of Pennsylvania) has prepared C-12 linear alkyl toluene (LAT).Being reflected at 2L is equipped with in mechanical stirrer, condenser and the dean stark trap round-bottomed flask of (being used for removing the water of reaction mixture) and carries out.(1000) CBV20A of the new roasting of about 50 grams is mixed with 920 gram SILVER REAGENT toluene, under appropriate stir speed (S.S.), stir, be heated to backflow.The vaporific toluene of about 25ml be collected in the water trap and from water trap, remove and make the reaction anhydrous.In 15 minutes, add about 168 gram α dodecylenes lentamente, continued stir about one hour down at 130～135 ℃.With reaction mixture cooling, filter, boil off excessive toluene and obtain thick alkyl toluene.At 150～155 ℃ and this thick material of 1～2mm vacuum under pressure distillation.Gas chromatographic analysis shows that it is the mixture that 2-tolyl isomer (84.20%), 3-tolyl isomer (15.77%) are made of ortho position, contraposition and meta-isomer, and para-isomeride is a primary product.

Embodiment 11

The preparation of high 2-position isomer C10-alkyl toluene

The C10-linear alkyl toluene (LAT) of having used mordenite CBV20A (contain/not fluoride) Preparation of Catalyst.That uses in reaction unit and the foregoing description 10 is identical.(1000) catalyzer of the new roasting of about 50 grams is mixed with 500 gram SILVER REAGENT toluene, under appropriate mechanical stirring, be heated to backflow.About 25ml toluene is collected into water trap and makes reaction mixture anhydrous.In 15 minutes, add about 140 gram C10-α alkene lentamente, under 120～130 ℃, under agitation heated cooled and filtered 30 minutes.Boil off excessive toluene, this thick alkyl toluene of vacuum distilling under 145～150 ℃ and 1～2mm.Gas chromatographic analysis distillatory cut shows that it is the mixture of 2-tolyl isomer (84.04%), 3-tolyl isomer (15.78%), each self-contained contraposition/ortho position/meta-isomer, and main isomer is a para-isomeride.

Embodiment 12

The preparation of high 2-position isomer lightweight alkyl toluene

The linear lightweight alkyl toluene (LLAT) of having used mordenite CBV20A Preparation of Catalyst.That uses in reaction unit and the foregoing description 10 is identical.(1000) CBV20A of the new roasting of about 50 grams are mixed with 400 gram SILVER REAGENT toluene, 120～125 ℃ with appropriate mechanical stirring under be heated to backflow.Remove about 25ml methylbenzene azeotropic thing and make react completely anhydrous.In 30 minutes, add the hydrocarbon mixture that about 600 grams contain about 10% alkene and 90% paraffin lentamente, continue about 2 hours of heating down at 130～135 ℃.With reaction mixture cooling, filter, remove excessive toluene and obtain thick alkyl toluene/mineral wax mixture.By at the most 250 ℃ down distillation remove deparaffnize.This finished product of distillation under 145～155C and 1～2mm pressure.The gas chromatographic analysis of distillatory product shows that it is the mixture of C10-C13 alkyl toluene, only contains the 2-and the 3-phenyl isomer of contraposition/ortho position/meta-isomer.

Composition with enhanced water hardness patience

When application has the LAB sulfonate of high 2-phenyl isomer content in following various cleaning formulations, unexpectedly observe the surprising observations of the water hardness patience of increase.The chemical field those of ordinary skill is known, and most of common " tap water " contain the alkaline earth metals calcium and the magnesium cation of different amounts.People know that these metals and most of soap and washing composition molecule (the LAB sulfonate material that comprises prior art) form more insoluble complex compound (a.k.a. " soap scum ").Such complexing action often causes combining the salt precipitation that forms with the material that is commonly used for soap by above-mentioned positively charged ion, and such complexing action causes the precipitation of complex compound, follows the total concn that washing composition in the solution takes place to effectively reduce.In the area of for example Texas, this is an annoying especially problem, and locality water supply there may contain calcium and the magnesium hardness up to 0.10%, and it is useless that it goes up some soap and washing composition substantially.In order to reduce the effect of hardness, formulator must often add a kind of sequestrant, for example, and one of borax, zeolite, citric acid or EDTA or its sodium salt, thereby form stable, soluble complexes with hard mineral substance, so cover or reduce effectively the effective concentration of hard mineral substance.

Be surprised to find that, usually by as above-mentioned complexing action hinder the active ionic type metal species of washing composition (for example, alkaline earth metal cation) and the LAB sulfonate with high 2-phenyl isomer content provided herein to form in the preparation that insoluble complex provides not as they and prior art LAB sulfonate easy like that.The net result that these class ionic metal species are difficult to form with LAB sulfonate with high 2-phenyl isomer provided by the invention and preparation described herein insoluble complex is, there is the active de-sludging component of this class of greater concn effectively in the solution, and can be used for the solubilising and the exposed base material of whole cleaning of oil.Should the results were quite startling because before the hard mineral substance since they form the tendency of insoluble salt with tensio-active agent and be the problem of preparing in various washing composition and the cleaning compositions always.So preparation of the present invention is initiative with regard to this respect, because first key step of alkaline earth metal cation as the problem in the preparation of washing composition etc. do not considered in their representatives.

Yet the LAB sulfonate of the present invention that has than the higher 2-phenyl isomer content that can obtain from prior art enlightenment in the past also has a Krafft temperature (length that depends on alkyl chain) in about 15 ℃～30 ℃ scopes.Under the situation of not wishing high like this Krafft temperature, these LAB may not be the selection materials when considering all situations.But, find that of the present invention LAT sulfonate of 2-phenyl isomer content in about 30.00%～80.00% scope has much lower Krafft temperature, usually less than 10 ℃, in-5 ℃～+ 5 ℃ scopes of the pact of more being everlasting.These lower Krafft temperatures are of value to provides the required micellar structure of acceptable de-sludging characteristic in the great majority application; Yet the water hardness patience of high 2-toluyl isomer LAT material depends on the alkyl chain length in the LAT material especially.As can be seen from Fig. 10, when the mean alkyl chain length of LAT material is lower than approximately 10.8 the time, water hardness patience is better than the LAB material.But, when mean alkyl chain length greater than about 11 the time, water hardness patience is just poor than the LAB material.So found, useful in some preparation is the mixture of using high 2-phenyl isomer LAT material and high 2-phenyl isomer LAB material, so that obtain a kind of combination that can be used in the detergent formulation, it more has enhanced de-sludging characteristic and water hardness patience highly under the low temperature.

By utilizing the component with high 2-phenyl isomer content provided herein, formulator can save the sequestrant in their preparation, the amount that perhaps at least only need suitably, reduces under many circumstances.Because such sequestrant is expensive, consider that from the angle of batching and material quantity the saving in the production can benefit the community.

Utilizing the 2-phenyl isomer content to be about 80% alkylbenzene sulfonate of the present invention replaces the 2-phenyl isomer content to have much bigger cleaning power usually less than about 50% those cleaning compositions.The enhancing of the clean-up performance that provides by the linear alkyl benzene sulfonate of the present invention with 2-phenyl isomer content (" superelevation 2-phenyl ") of about 80% has been provided below by the data among Fig. 5.In Fig. 5, from the performance of laundry test data set forth the superelevation 2-phenyl that contains different additions, comprised conventional linear alkyl benzene sulfonate (represent with A225, its 2-phenyl isomer content account for existence total alkylbenzene sulfonate about 16%～18%; A225 can derive from and be positioned at 7114 North Lamar Blvd., Austin, the HuntsmanPetrochemical Corporation of Texas) total detergency of adulterant.In this campaign,, keep the active substance total amount constant 10% with superelevation 2-phenyl and A225 fusion.Under 100 °F, in 6pot Terg-o-tometer  (US Testing Corporation),, use 150ppm hard water with 2 gram washing composition/liter test, take 15 minutes cycles of washing, follow rinsing in 5 minutes.Utilize stdn dirt swatch to assess detersive power.Before and after washing, utilize Hunter Lab Color Quest reflexometer (adopting the L-A-B scale), obtained the result by the reflectance of measuring little cloth sheet.All the cloth sheets are all with triplicate test and be averaged the result.The dirt cloth sheet of using is: dirty motor oil, sebum bits (dust sebum), meadow stain (grass stain), blood/milk/ink spot, sweet oil (EMPA), clay and mensuration deposit the clean calico sheet of usefulness again.Assess all dirts with cotton and polyester/cotton blended fabric.The result shows that cleaning capacity strengthens with the increase of 2-phenyl isomer percentage composition in the adulterant.Using 100%, to contain the washing composition result of material of high 2-phenyl isomer content higher by 50% than conventional linear alkyl benzene sulfonate (" LAS ").Be used for the complete soln of hardness test at this paper, adopt 2: 1 calcium: the magnesium ratio.

As mentioned above, utilize the washing composition of superelevation 2-phenyl preparation to show bigger patience to the water hardness with respect to those that prepare with conventional commercially available linear alkyl benzene sulfonate de-sludging component.

Fig. 6 hereinafter provides the turbidity data, in order to confirm (to use from Orbeco-Helige of Farmingdale with NTU unit, the turbidometer of NY) measure, be conventional LAS surfactant A 225 that about 1% aqueous solution the exists hardness patience when different water hardness level, its application is that those of ordinary skills know.In Fig. 6, it is the point that roughly is equivalent to by seeing the solubility limit of the complex compound that hard mineral substance in the water and de-sludging component form that solution turbidity at first experiences selecting of rapid increase.So, use the preparation of conventional linear alkyl benzene sulfonate component (being similar to A225) when the water hardness level of about 750ppm, to begin to experience the reduction of main ingredient effective concentration.Certainly, for hope by in the water of given volume, using user than suggestion amount soap still less, this effect will be more remarkable more, because the amount of total hardness will greatly increase with respect to obtainable sulfonate, it may be in some cases in conjunction with more than half sulfonate that exists.

When Fig. 7 provides and has existed with about 1% aqueous solution and the data of Fig. 6 same rigidity patience data of collecting; But, the LAS that uses in order to collect these data is superelevation 2-phenyl LAS.As seen data from Fig. 7 also do not form the water-insoluble compound of significant quantity when reaching the firmness level of about 1500ppm, it is about twice of the hardness patience of conventional substances.Because preparation of the present invention contains the 2-phenyl isomer of high-load linear alkyl benzene sulfonate, they not only have the detergency of increase, and more water-fast hardness.So, in preparation available still less active chemical and give its and contain detergency that the prior art preparation of more substantial linear alkyl benzene sulfonate equates.The amount that reduces active chemical in the preparation has been saved raw materials cost, fusion running cost and transportation cost, and these savings can make popular being benefited.

Fig. 8 provides the data with Fig. 6 and the 7 same rigidity patience data of collecting; But, surfactant concentration is reduced to the influence of the surfactant concentration that about 0.1% aqueous solution reduces with demonstration, because begin to form the tensio-active agent total amount that sedimentary point depends on existence.In Fig. 8, compared the alkylbenzene sulfonate of A225 and the 2-of having phenyl isomer content provided by the invention.From these data as seen, use conventional A225 material, when the firmness level of about 25ppm, just form the water-insoluble compound of significant quantity, and superelevation 2-phenyl material even when four times of firmness levels (or reaching about 100ppm), also do not show any precipitation.

Fig. 9 has explained the unexpected synergy of finding about the adulterant that contains linear alkyl benzene sulfonate and linear alkyl tosylate, and wherein, this two classes sulfonated aromatic alkylide all has the 2-phenyl isomer content greater than 75%.Data on the figure are that (hardness is 300ppm, Ca/Mg=2: NTU turbidity value 1), the adulterant in the solution contain these linear alkyl benzene sulfonates (SLAS) and the linear alkyl tosylate (SLATS) of different amounts to 0.10% aqueous solution.For each data point, when 0.10% total solution, total combined amount of tensio-active agent is identical.When the amount of the alkyl toluene sulfonate that exists accounts for tensio-active agent total amount about 15%～55% time of existence, from scheming to go up visible unexpected minimum value.

Because the preparation of this various cleaning compositions in a large number comprises the linear alkyl benzene sulfonate as main de-sludging component, the application range that the present invention finds is very big really.So, can prepare efficient and the cleaning power that increases all cleaning compositions well known in the prior art, as to contain the linear alkylbenzene of sulfonation again by following method, that is the linear alkylbenzene of sulfonation that replaces at least a portion to use at present with the linear alkyl toluene tensio-active agent of sulfonation provided by the invention (it has a bigger percentage composition 2-phenylalkyl toluene isomer than available in the past).In addition, because the LAT sulfonate with high 2-phenyl isomer content (the order of magnitude) and conventional LAB or the fusion of LAT sulfonate that can produce by the present invention about 82%, also can provide blended LAB/LAT sulfonate component by the present invention, it is applicable to and forms a kind of de-sludging composition or cleaning formulation, wherein, the 2-phenyl isomer content that has of component is any set point value between about 18wt%～82wt% based on the whole isomer sum totals and the weight of LAB that exists and LAT sulfonate.As shown in Figure 5, utilize Catalyst Production 2-phenyl isomer content of the present invention to surpass 80% alkylbenzene by method of the present invention easily.

The finished product detergent formulations preferably utilizes the tensio-active agent based on LAB of 2-phenyl isomer content in about 30～40% scopes, but does not also reach described content with the commercialization amount so far.By utilizing the present invention, realize comprising the LAB with 30%～40%2-phenyl isomer and the various cleaning product of LAT sulfonate at commercial size first easily.Hereinafter provided some and utilized the embodiment of the linear alkylbenzene of sulfonation as the good preparation of tensio-active agent.In each embodiment, the LAB sulfonate of application and LAT sulfonate all are the sulfonate of producing by table 2, and have about 81% 2-phenyl isomer content.In these embodiments, a kind of LAB sulfonate of term " LAB sulfonate " expression with 80%2-phenyl content, it has based on the whole LAB sulfonate isomer total amounts that exist in this LAB sulfonate is 80% 2-phenyl isomer content.A kind of LAT sulfonate of term " the LAT sulfonate with 80%2-phenyl content " expression, it has based on the whole LAT sulfonate isomer total amounts that exist in this LAT sulfonate is 80% 2-phenyl isomer content.Among each embodiment that provides hereinafter, whole components are merged remix each other until evenly.So, under each situation, as required, utilize the NaOH and the HCl aqueous solution to regulate the pH of final mixture (as carrying out) to 10～11 scopes according to the preferred form of the present invention.Yet, can realize any final pH level in about 7～12 scopes.In the liquid disk washing liquid, wish the pH in about 7～8 scopes most.

As seen, in each prescription, there is the component except that alkylbenzene tensio-active agent among the embodiment hereinafter with high 2-phenyl isomer content.These other components all are known preparation soap, cleaning compositions, hard surface cleaner, the scouring agent etc. of being applicable to of those of ordinary skills.With regard to the present invention and appended claims, term " known other component that is applicable to preparation soap, washing composition etc. " the such arbitrary substance of expression, promptly, soap or detergent applications regular convention formula Designers think and add and be of value to physicals, the fragrance or attractive in appearance of wishing as the mixture of cleaning compositions, no matter the base material that will clean how.Such material comprises known each material that is applicable to soap and detergent formulation of prior art.

Among each embodiment hereinafter, unless otherwise indicated, all percentage ratios all provide with the weight percentage based on the final product composition having gross weight.

Embodiment 13-all purpose cleaner

LAT sulfonate 1.3 with 80%2-phenyl content

LAB sulfonate 2.0 with 80%2-phenyl content

Alkyl-sulphate 1.6

Coco-nut oil fatty acid 1.8

Monoethanolamine 1.5

SURFONICL12-6??????????????????????????????12.4

Amine oxide 0.9

SODA ASH LIGHT 99.2 0.7

Water 77.8

Amount to 100

Embodiment 14-all purpose cleaner

LAT sulfonate 0.66 with 80%2-phenyl content

LAB sulfonate 2.64 with 80%2-phenyl content

Alkyl-sulphate 1.6

Coco-nut oil fatty acid 1.8

Monoethanolamine 1.5

SURFONICL12-6????????????????????????????12.4

Amine oxide 0.9

SODA ASH LIGHT 99.2 0.7

Water 77.8

Amount to 100

Embodiment 15-all purpose cleaner

LAT sulfonate 0.66 with 80%2-phenyl content

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 2.64

Alkyl-sulphate 1.6

Coco-nut oil fatty acid 1.8

Monoethanolamine 1.5

SURFONICL12-6????????????????????????????????12.4

Amine oxide 0.9

SODA ASH LIGHT 99.2 0.7

Water 77.8

Amount to 100

Embodiment 16-pine tar microemulsion

Pine tar 20.0

SURFONICL12-8????????????????????????????????4.7

LAT sulfonate 3.12 with 80%2-phenyl content

LAB sulfonate 4.68 with 80%2-phenyl content

Virahol 11.0

Trolamine 4.7

Water 51.8

Amount to 100

Embodiment 17-pine tar microemulsion

Pine tar 20.0

SURFONICL12-8?????????????????????????????4.7

LAT sulfonate 1.56 with 80%2-phenyl content

LAB sulfonate 6.24 with 80%2-phenyl content

Virahol 11.0

Trolamine 4.7

Water 51.8

Amount to 100

Embodiment 18-pine tar microemulsion

Pine tar 20.0

SURFONICL12-8?????????????????????????????4.7

LAT sulfonate 1.56 with 80%2-phenyl content

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 6.24

Virahol 11.0

Trolamine 4.7

Water 51.8

Amount to 100

Embodiment 19-is worth brand (Value Brand) washing powderB

LAB sulfonate 3.9 with 80%2-phenyl content

LAT sulfonate 2.6 with 80%2-phenyl content

SURFONICN-95????????????????????????????????4.3

SODA ASH LIGHT 99.2 29.8

Sodium-chlor 45.7

Water glass 11.6

Polymkeric substance 2.1

Embodiment 20-is worth brand washing powder

LAB sulfonate 5.2 with 80%2-phenyl content

LAT sulfonate 1.3 with 80%2-phenyl content

SURFONICN-95????????????????????????????????4.3

SODA ASH LIGHT 99.2 29.8

Sodium-chlor 45.7

Water glass 11.6

Polymkeric substance 2.1

Embodiment 21-is worth brand washing powder

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 3.9

LAT sulfonate 2.6 with 80%2-phenyl content

SURFONICN-95????????????????????????????????4.3

SODA ASH LIGHT 99.2 29.8

Sodium-chlor 45.7

Water glass 11.6

Polymkeric substance 2.1

Embodiment 22-Premium Brands (Premium Brand) washing powder

LAB sulfonate 5.68 with 80%2-phenyl content

LAT sulfonate 1.42 with 80%2-phenyl content

Sodium alkyl sulfate 13.3

Fatty alcohol ethoxylate 2.6

Zeolite 34.7

SODA ASH LIGHT 99.2 19.6

Water glass 1.0

Sodium peroxoborate 0.9

TAED????????????????????????????????????0.5

Sodium sulfate 19.3

Proteinase-10 .5

Cellulase 0.5

Amount to 100

Embodiment 23-Premium Brands washing powder

LAB sulfonate 4.26 with 80%2-phenyl content

LAT sulfonate 2.84 with 80%2-phenyl content

Sodium alkyl sulfate 13.3

Fatty alcohol ethoxylate 2.6

Zeolite 34.7

SODA ASH LIGHT 99.2 19.6

Water glass 1.0

Sodium peroxoborate 0.9

TAED????????????????????????????????????0.5

Sodium sulfate 19.3

Proteinase-10 .5

Cellulase 0.5

Amount to 100

Embodiment 24-Premium Brands washing powder

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 4.26

LAT sulfonate 2.84 with 80%2-phenyl content

Sodium alkyl sulfate 13.3

Fatty alcohol ethoxylate 2.6

Zeolite 34.7

SODA ASH LIGHT 99.2 19.6

Water glass 1.0

Sodium peroxoborate 0.9

TAED??????????????????????????????????????????0.5

Sodium sulfate 19.3

Proteinase-10 .5

Cellulase 0.5

Amount to 100

Embodiment 25-is worth brand laundry enriched material

LAB sulfonate 11.1 with 80%2-phenyl content

LAT sulfonate 7.4 with 80%2-phenyl content

SURFONICN-95????????????????????????????????75.00

Monoethanolamine 6.50

Amount to 100

Embodiment 26-is worth brand laundry enriched material

LAB sulfonate 14.8 with 80%2-phenyl content

LAT sulfonate 3.7 with 80%2-phenyl content

SURFONICN-95????????????????????????????????75.00

Monoethanolamine 6.50

Amount to 100

Embodiment 27-is worth brand laundry enriched material

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 14.8

LAT sulfonate 3.7 with 80%2-phenyl content

SURFONICN-95?????????????????????????????????75.00

Monoethanolamine 6.50

Amount to 100

Embodiment 28-is worth the brand scouring agent

Enriched material 7.0000 from embodiment 22,23 or 24

Water (well water) 92.168

White dyes 0.0100

Salt 0.1352

Salt 0.6148

Sanitas 0.0100

Dyestuff 0.0020

Spices 0.0600

Amount to 100

Embodiment 29-is worth brand laundry enriched material

LAB sulfonate 10.44 with 80%2-phenyl content

LAT sulfonate 7.00 with 80%2-phenyl content

SURFONICN-95?????????????????????????????34.8

SURFONICT-15?????????????????????????????17.4

POGOL300?????????????????????????????????8.0

Monoethanolamine 2.4

Water 20.0

Amount to 100

Embodiment 30-is worth brand laundry enriched material

LAB sulfonate 13.92 with 80%2-phenyl content

LAT sulfonate 3.48 with 80%2-phenyl content

SURFONICN-95??????????????????????????????34.8

SURFONICT-15??????????????????????????????17.4

POGOL300??????????????????????????????????8.0

Monoethanolamine 2.4

Water 20.0

Amount to 100

Embodiment 31-is worth brand laundry enriched material

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 13.92

LAT sulfonate 3.48 with 80%2-phenyl content

SURFONICN-95?????????????????????????????????34.8

SURFONICT-15?????????????????????????????????17.4

POGOL300?????????????????????????????????????8.0

Monoethanolamine 2.4

Water 20.0

Amount to 100

Embodiment 32-is worth the brand scouring agent

Enriched material 50.000 from embodiment 26,27 or 28

Water 44.245

White dyes A 0.15

Sodium-chlor 0.500

Polyacrylate A 2.500

Sequestrant 1.00

NaOH(50.0％aq.)????????????????????????????????0.220

Spices 0.300

Sanitas 0.080

Oils,Melaleuca leucadendron 0.005

Amount to 100

Embodiment 33-contains enzyme high-quality scouring agent

Enriched material 30.0000 from embodiment 30,31 or 32

Water (well water) 56.2632

White dyes 0.0500

U-Ramin MC 0.1000

Sodium-chlor 0.6148

Sanitas 0.0100

Dyestuff 0.0020

Spices 0.0600

Propylene glycol 10.0000

Borax 2.0000

Proteinase-10 .7000

Lipase 0.2000

Amount to 100

The liquid dishwashing preparation of embodiment 34-high-quality I

LAB sulfonate 15.44 with 80%2-phenyl content

LAT sulfonate 10.31 with 80%2-phenyl content

Deionized water 16.316

Magnesium hydroxide 1.133

Sodium hydroxide (38% aqueous solution) 3.591

SURFONIC  SXS-40 (40% aqueous solution) 15.000

Propylene glycol 6.000

Sodium lauryl tri(oxyethyl) sulfate (3 moles of EO, 70% aqueous solution) 14.286 (molecular weight=440)

AMONYL 380LC (38% aqueous solution) 15.789

Ethanol 0.0300

EDTA four sodium 0.1500

Sanitas 0.2000

Dyestuff (0.8% aqueous solution) 1.0000

Spices 0.5000

Amount to 100

The liquid dishwashing preparation of embodiment 35-high-quality

LAB sulfonate 20.59 with 80%2-phenyl content

LAT sulfonate 5.16 with 80%2-phenyl content

Deionized water 16.316

Magnesium hydroxide 1.133

Sodium hydroxide (38% aqueous solution) 3.591

SURFONIC  SXS-40 (40% aqueous solution) 15.000

Propylene glycol 6.000

Sodium lauryl tri(oxyethyl) sulfate (3 moles of EO, 70% aqueous solution) 14.286 (molecular weight=440)

AMONYL 380LC (38% aqueous solution) 15.789

Ethanol 0.0300

EDTA four sodium 0.1500

Sanitas 0.2000

Dyestuff (0.8% aqueous solution) 1.0000

Spices 0.5000

Amount to 100

The liquid dishwashing preparation of embodiment 36-high-quality

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 20.59

LAT sulfonate 5.16 with 80%2-phenyl content

Deionized water 16.316

Magnesium hydroxide 1.133

Sodium hydroxide (38% aqueous solution) 3.591

SURFONIC  SXS-40 (40% aqueous solution) 15.000

Propylene glycol 6.000

Sodium lauryl tri(oxyethyl) sulfate (3 moles of EO, 70% aqueous solution) 14.286 (mw=440)

AMONYL 380LC (38% aqueous solution) 15.789

Ethanol 0.0300

EDTA four sodium 0.1500

Sanitas 0.2000

Dyestuff (0.8% aqueous solution) 1.0000

Spices 0.5000

Amount to 100

The liquid dishwashing preparation of embodiment 37-high-quality

LAB sulfonate 6.12 with 80%2-phenyl content

LAT sulfonate 4.08 with 80%2-phenyl content

Deionized water 35.567

Magnesium hydroxide 1.133

Sodium hydroxide (38% aqueous solution) 1.250

SURFONIC  SXS-40 (40% aqueous solution) 15.000

Propylene glycol 6.000

Sodium lauryl tri(oxyethyl) sulfate (40% aqueous solution) 20.000 (molecular weight=440)

Alkyl polyglycoside (50% aqueous solution) 6.000

Lipid acid MEA acid amides 3.000

EDTA four sodium 0.150

Sanitas 0.200

Spices 0.500

Amount to 100

The liquid dishwashing preparation of embodiment 38-high-quality

LAB sulfonate 8.16 with 80%2-phenyl content

LAT sulfonate 2.04 with 80%2-phenyl content

Deionized water 35.567

Magnesium hydroxide 1.1 33

Sodium hydroxide (38% aqueous solution) 1.250

SURFONIC  SXS-40 (40% aqueous solution) 15.000

Propylene glycol 6.000

Sodium lauryl tri(oxyethyl) sulfate (40% aqueous solution) 20.000 (molecular weight=440)

Alkyl polyglycoside (50% aqueous solution) 6.000

Lipid acid MEA acid amides 3.000

EDTA four sodium 0.150

Sanitas 0.200

Spices 0.500

Amount to 100

The liquid dishwashing preparation of embodiment 39-high-quality

The 2-phenyl content is 12.0%～30.0% LAB sulfonate 8.16

LAT sulfonate 2.04 with 80%2-phenyl content

Deionized water 35.567

Magnesium hydroxide 1.133

Sodium hydroxide (38% aqueous solution) 1.250

SURFONIC  SXS-40 (40% aqueous solution) 15.000

Propylene glycol 6.000

Sodium lauryl tri(oxyethyl) sulfate (40% aqueous solution) 20.000 (molecular weight=440)

Alkyl polyglycoside (50% aqueous solution) 6.000

Lipid acid MEA acid amides 3.000

EDTA four sodium 0.150

Sanitas 0.200

Spices 0.500

Amount to 100

Embodiment 40-powdery aircraft sanitising agent

Metso pentabead 20 (water glass) 30.0

Tri sodium Phosphate 30.0

Ammonium bifluoride 8.0

Tetrasodium pyrophosphate 20.0

LAB sulfonate 4.0 with 80%2-phenyl content

LAT sulfonate 8.0 with 80%2-phenyl content

Embodiment 41-powdery aircraft sanitising agent

Metso pentabead 20 (water glass) 30.0

Tri sodium Phosphate 30.0

Ammonium bifluoride 8.0

Tetrasodium pyrophosphate 20.0

LAB sulfonate 8.0 with 80%2-phenyl content

LAT sulfonate 4.0 with 80%2-phenyl content

Embodiment 42-powdery aircraft sanitising agent

Metso pentabead 20 (water glass) 30.0

Tri sodium Phosphate 30.0

Ammonium bifluoride 8.0

Tetrasodium pyrophosphate 20.0

LAB sulfonate 8.0 with 80%2-phenyl content

LAT sulfonate 4.0 with 80%2-phenyl content

Embodiment 43-dairy farm sanitising agent

Sodium hexametaphosphate 99 20.00

Sodium sulfate 20.00

LAB sulfonate 30.00 with 80%2-phenyl content

LAT sulfonate 10.00 with 80%2-phenyl content

Embodiment 44-dairy farm sanitising agent

Sodium hexametaphosphate 99 20.00

Sodium sulfate 20.00

LAB sulfonate 10.00 with 80%2-phenyl content

LAT sulfonate 30.00 with 80%2-phenyl content

Embodiment 45-powdered milk field sanitising agent

LAB sulfonate 3.00～50.00 with 80%2-phenyl content

LAT sulfonate 3.00～50.00 with 80%2-phenyl content

Sodium sulfate 0.00～20.00

Water glass 0.00～30.00

Nonionic surface active agent 5.00

The neutral dairy farm of embodiment 45-powdery sanitising agent

LAB sulfonate x (wherein, x=0.00～33.00) with 80%2-phenyl content

LAT sulfonate 33-x with 80%2-phenyl content

Nonionic surface active agent 1.00

Monsanto?Phosphate?STP/A??????????????????33.00

Monsanto?Phosphate?SAPP/A?????????????????33.00

Embodiment 46-motor vehicle sanitising agent, powder

Tri sodium Phosphate 36.0

Tetrasodium pyrophosphate 30.0

Anhydrous sodium metasilicate 20.0

LAT sulfonate 5.0 with 80%2-phenyl content

Shell?Chemical?Co.Neodol?91-6?????????????8.00

Monsanto Co.Dequest 2006 phosphonates 1.00

Embodiment 47-aluminium motor vehicle sanitising agent, powder

Tri sodium Phosphate 36.00

Tetrasodium pyrophosphate 30.00

Anhydrous sodium metasilicate 20.00

LAB sulfonate 5.00 with 80%2-phenyl content

Shell?Chemical?Co.Neodol?91-6?????????????8.00

Monsanto Co.Dequest 2006 phosphonates 1.00

The foregoing description is intended to enumerate the versatility of composition aspect family expenses preparation and commercial cleaning formulation that the present invention produces, and in no case wants to limit it.Any preparation of soap, washing composition, cleaning compositions, no matter be liquid or solid, desired use that let it be how, in its common dosage forms, comprise LAB sulfonate as a kind of component, can increase its effectiveness by following method, promptly, remove present merchant LAB sulfonate component used in its preparation, what replace it is a kind of such component: the LAB sulfonate component and the LAT sulfonate component with 2-phenyl isomer content of rising that comprise the 2-phenyl isomer content with rising.So the present invention represents the revolutionary character progress in the detergent applications, because preferred 2-phenyl isomer that now can high yield production aromatic alkylate, and overall cost and relatively poor prior art LAB sulfonate mixtures is much the same.

In previous formulations, LAB sulfonate than the relative ratios of LAT sulfonate in 1.5: 1～4: 1 scopes.This owing to we find, about the LAB sulfonate that exists in the water-detergent solution that contains these materials unexpected synergy than the relative quantity of LAT sulfonate.Diagram has been described our discovery among Fig. 9.

Also found, at room temperature can be used as solids separation 2-phenyl isomer content greater than about 60% alkylbenzene sulfonate.This result is unexpected, because think that so far alkylbenzene sulfonate only exists with liquid form.So, by the present invention, can provide the dry powder formulation that comprises alkylbenzene sulfonate now, for example, do scouring agent, the agent of dry-cleaning dish etc.Such dry preparation can be used existing fusion technology and provide, and comprises that (for example, ribbon blender etc.) application also comprises the detergent tablet of the usefulness of doing washing to conventional dry process equipment.

Solid alkylbenzene salt as for production preferred form of the present invention, begin to use azochlorosulfonate acid mixture, it is produced from the sulfonation by the alkylbenzene mixture of the present invention preparation, for example goes up any of sample 4～7 in the table 2, and they contain the 2-phenyl isomer greater than about 80.0%.Then, with the water-soluble concentration of this sulfonic acid to about 10.0wt%, then neutralize, up to the stoichiometric point of neutralization (being to reach about 10.5 time under the situation of sodium and potassium) occurring as pH by the alkali aqueous solution (for example) that slowly adds required cationic by utilizing alkali metal hydroxide.At last, remove and anhydrate by evaporation or chemical field other method known to the skilled, for example, by utilizing ROTOVAP  vaporizer etc., spray-dryer, turbo driers etc. are so stay the alkylbenzene sulfonate crystal.This crystal is the purifying by recrystallization from ethanol easily.The alkyl benzene sulphonate (ABS) sodium salt of sample 4 and sylvite have a fusing point in the table 2 in about 50 ℃～80 ℃ scopes, and it depends on alkyl chain length, and chain length is longer, and the fusing point of material is higher.The used test method is the dsc of ASTM standard D-3417.

Cationic surfactant also plays cation sites when forming stable solid alkylbenzene sulfonates.Cationic surfactant is well known in the art, and they are the tensio-active agents that have positively charged radical ion in its molecular structure, for example, and quaternary ammonium compound.Known cationic surfactant works the capillary effect that reduces water with the other parts of the detergent system of preparation.They are generally used for washing, rinsing and having added in the fabric softener of siccative.So, when in solid alkylbenzene sulfonates of the present invention, providing charge balance when using a kind of cationic surfactant, use the formulator of this salt can be from identical solid matter (it can be worn into powder) cationic surfactant and aniorfic surfactant the two existence and obtain extra benefit.Therefore, such salt can reduce the expense relevant with the fusion different substances with common in the art storage, and this is because with the cause that had not only had tensio-active agent but also had washing composition in a kind of molecule.

Because this unexpected discovery, promptly, some alkylbenzene sulfonate with enough 2-phenyl isomer content at room temperature is a solid, the present invention also comprises the preparation (it comprises solid piece) that is applicable to the cleaning clothes, and comprises the solid bar shaped soap as the solid alkylbenzene sulfonates of active de-sludging component.

For example in the following document detergent tablet: GB 911 204 (Unilever) is being described, U.S. Patent No. 3,953,350 (Kao), JP 60 015 500A (Lion), JP 60 135 497A (Lion) and JP 60 135 498A (Lion); Also has the detergent tablet of selling in Spain.Well known, detergent tablet is normally by compression or compress that scrubbing powder makes.So the present invention expects with the active de-sludging component of the conventional laundry of alkylbenzene sulfonate replacement at least a portion (and more preferably whole) prior art sheet with enough high 2-phenyl isomer, thereby causes this salt at room temperature to exist with solid form.Substituting easily like this undertaken by the conventional de-sludging component that provides this solid sulfoacid salt to substitute conventional laundry sheet in laundry sheet production process.

The bar shaped soap is by the known prepared in various methods of this area people, and it comprises, before it fully saponified with caustic alkali/oil mixt impouring mould, perhaps by means of or need not heat and pressure in press, use " noodles shape soap ".Soap comprises fatty acid carboxylate salt, spices, dyestuff, sanitas, sterilant, filler (for example talcum) usually, and other additive.The present invention expects with the active cleaning component of the conventional bar shaped soap of alkylbenzene sulfonate replacement at least a portion (and the more preferably whole) prior art with enough high 2-phenyl isomer, thereby causes this salt at room temperature to exist with solid form.Substituting easily like this undertaken by the conventional de-sludging component that provides this solid sulfoacid salt to substitute conventional bar shaped soap in the soap production process.So, bar shaped soap of the present invention may only contain superelevation 2-phenylalkyl benzene sulfonate of the present invention, make up and form solid bar shaped soap with capacity tackiness agent, spices, dyestuff etc., in a form of the present invention, utilize to be applicable to the identical common compress technique of producing the sheet of doing washing.

Though illustrate and described the present invention about some embodiment preferred, obviously, others skilled in the art read and understood this specification sheets after can expect the variation and the modification that are equal to.The present invention includes all these variation that is equal to and modifications, and only be subjected to the restriction of claims scope hereinafter.

Claims (101)

1. the composition of matter that contains one or more sulfonated aromatic alkylide, said composition comprise the 2-phenyl isomer based on the sulfonated aromatic alkylide of being represented by following general formula of any amount of mixture total weight amount 30.00wt%～82.00wt%:

Wherein, n may equal 4～16 arbitrary integer, wherein, and R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be the base that is selected from sulfonic group or sulphonate-base, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be the substituting group that is selected from methyl and ethyl, described content comprises one of each percentage between two numerical value percentage ratio.

2. the composition of claim 1, wherein, the described 2-phenyl isomer that comprises based on any amount of mixture total weight amount 40.00%～70.00%, described content comprises one of each percentage between two numerical value percentage ratio.

3. the composition of claim 1, wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be sulphonate-base, and owing to existing one or more positively charged ions that are selected from down group to realize electric neutrality: the ammonium of sodium, potassium, lithium, rubidium, magnesium, calcium, strontium, ammonium, alkanol ammonium and alkyl replacement.

4. the composition of claim 3, wherein, described mixture is oxide compound, oxyhydroxide, silicate or the carbonate that utilizes the metal be selected from sodium, potassium, lithium, rubidium, magnesium, calcium and strontium, in the aqueous solution in and the sulfonated aromatic alkylide of claim 1 obtain.

5. the composition of claim 1, wherein, exist in the described mixture based on this mixture total weight amount R in the sulfonic acid of 50wt% at least ₃It is methyl.

6. the composition of claim 1, wherein, exist in the described mixture based on this mixture total weight amount R in the sulfonic acid of 50wt% at least ₃It is ethyl.

7. the composition of claim 1, wherein, exist in the described mixture based on this mixture total weight amount R in the 25wt% sulfonic acid at least ₃It is sulfonic group.

8. the composition of claim 1, wherein, the 2-phenyl isomer content of sulfonated aromatic alkylide accounts for any amount of the 45.00wt%～82.00wt% of described component gross weight, and described content comprises one of each percentage between two numerical value percentage ratio.

9. the composition of claim 1, wherein, the 2-phenyl isomer content of sulfonated aromatic alkylide accounts for any amount of the 57.00wt%～82.00wt% of described component gross weight, and described content comprises one of each percentage between two numerical value percentage ratio.

10. the composition of claim 1, wherein, the alkyl that is connected on the aromatic ring roughly is linear.

11. the composition of claim 10, wherein, described alkyl contains an arbitrary integer carbon atom of 7～16.

12. the composition of claim 1, wherein, the alkyl that is connected on the aromatic ring is a branched-alkyl.

13. the composition of claim 12, wherein, described alkyl contains an arbitrary integer carbon atom of 7～16.

14. the composition of claim 1, it further comprises the known preparation soap that is applicable to, the other material of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, citric acid, Citrate trianion, nitrilo acetate, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, water-soluble branched-alkyl benzene sulfonate, ether sulfate, the alkyl phenolic alkoxy thing, fatty acid amide, alhpa olefin sulfonate, paraffin sulfonate, betaine, sequestrant, tallow amine ethoxylate, polyetheramine ethoxylate, the ethylene oxide/propylene oxide segmented copolymer, fatty alcohol ethylene epoxide/propylene oxide low-foaming surfactant, methyl ester sulfonate, alkyl polysaccharide, the N-methyl glucose amide, alkylation sulfonation phenyl ether, polyoxyethylene glycol, and the 2-phenyl isomer content is less than 30.00% water-soluble alkylbenzene sulfonate.

15. the composition of claim 14, wherein, described other material is the mixture of water-soluble alkylbenzene sulfonate, wherein, the 2-phenyl isomer content of described water-soluble alkylbenzene sulfonate based on described other material gross weight less than 25.00wt%.

16. the composition of claim 14, wherein, described sulfonated aromatic alkylide accounts for any amount of the 1.00wt%～25.00wt% of total composition weight.

17. the composition of claim 14, wherein, described other material exists with any amount based on the 0.10wt%～25.00wt% of described mixture total weight amount.

18. the composition of claim 14, it further comprises the third component, wherein, described the third component is different from described second kind of component and is selected from down the group material: at least a known preparation soap that is applicable to, other component of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, water-soluble branched-alkyl benzene sulfonate, and the 2-phenyl isomer content is less than 30.00% water-soluble alkylbenzene sulfonate.

19. the composition of claim 18, wherein, described the third component is the mixture of water-soluble alkylbenzene sulfonate, wherein, the 2-phenyl isomer content of described water-soluble alkylbenzene sulfonate based on described water-soluble alkylbenzene sulfonate component gross weight less than 25.00wt%.

20. the water-soluble salt of the composition of claim 1, they at room temperature are solids, and they comprise at least a negatively charged ion that is selected from down group: sodium, potassium, calcium and magnesium.

21. an alkyl toluene sulfonate, wherein, described salt at room temperature exists with solid form.

22. contain the composition of matter of the mixture of alkyl toluene sulfonate, wherein, described alkyl toluene sulfonate comprises single alkyl substituent, this alkyl substituent be connected on the phenyl ring that has also connected a sulphonate-base, that be selected from any carbonatoms of having in the de-sludging scope those, wherein, the 2-phenyl isomer content of such alkyl toluene sulfonate is enough to make such salt mixture at room temperature to exist with solid form.

23. the salt mixture of claim 22, recording it by dsc by ASTM method D-3417 does not have the fusing point peak in 60 ℃～90 ℃ scopes.

24. the salt mixture of claim 22, wherein, described salt comprises a kind of positively charged ion that is selected from down group: alkali metal cation, alkaline earth metal cation, ammonium ion, and cationic surfactant.

25. the mixture of the alkyl toluene sulfonate of claim 24, wherein, described positively charged ion is selected from sodium and potassium.

26. a solid bar shaped soap, it comprises the 2-phenyl isomer of 3.99wt%～25.00wt% alkyl toluene sulfonate, and wherein, at least 50% of the alkyl toluene sulfonate isomer of existence is a 2-toluyl isomer.

27. mobile powdery de-sludging goods, it comprises solid alkyl toluene sulfonate and at least a known other component that is applicable to preparation soap, washing composition etc.

28. one kind is applicable to the solid piece of cleaning clothes, it comprises solid alkyl toluene sulfonate and at least a known other component that is applicable to preparation soap, washing composition etc.

29. one kind from comprising a) oil; B) water; And c) emulsion of the component of the composition of claim 1 formation.

30. the emulsion of claim 29, wherein, described emulsion is selected from O/w emulsion and water-in-oil emulsion.

31. the emulsion of claim 29, wherein, described emulsion comprises You Heshui, and wherein, oil exists with identical weight or meausurement with water.

32. an aqueous solution that comprises the composition of claim 1, wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be sulphonate-base, and wherein, the total amount of sulfonate is 0.09wt%～0.11wt% based on this total solution weight in the described aqueous solution, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 200 NTU units is provided in the described aqueous solution.

33. an aqueous solution that comprises the composition of claim 1, wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be sulphonate-base, and wherein, the total amount of sulfonate is 0.09wt%～0.11wt% based on this total solution weight in the described aqueous solution, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 100 NTU units is provided in the described aqueous solution.

34. an aqueous solution that comprises the composition of claim 1, wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be sulphonate-base, and wherein, the total amount of sulfonate is 0.09wt%～0.11wt% based on this total solution weight in the described aqueous solution, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 50 NTU units is provided in the described aqueous solution.

35. one kind is applicable to that preparation is used for the composition of de-sludging composition finished product of clean textile, dish, crust and other base material, it is made of following component:

A) the first kind of component that exists with any amount based on mixture total weight amount 99.75wt%～0.25wt%, described first kind of component is characterised in that, it comprises the mixture of two or more water-soluble sulfonates, and this mixture comprises the 2-phenyl isomer of the sulfonated aromatic alkylide of being represented by following general formula based on any amount of this mixture total weight amount 30.00wt%～82.00wt%:

Wherein, n can equal 4～16 arbitrary integer, wherein, and R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be selected from sulfonic group or sulphonate-base, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be the substituting group that is selected from methyl and ethyl, wherein said content comprises one of each percentage between two numerical value percentage ratio;

And

B) the second kind of component that exists with any amount based on mixture total weight amount 0.25wt%～99.75wt%, described second kind of component is characterised in that, it comprises the water-soluble sulfonate of the 2-phenyl isomer of the alkylbenzene of being represented by following general formula based on any amount of described second kind of component gross weight 26.00wt%～82.00wt%, wherein, described content comprises one of each percentage between two numerical value percentage ratio:

Wherein, the arbitrary integer that n equals 4～16, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In any but have only one to be selected from sulfonic group or sulphonate-base, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In be not that those of sulfonic group or sulphonate-base all are hydrogen.

36. the composition of claim 35, wherein, the content of 2-phenyl isomer accounts for any amount of 45.00wt%～82.00wt% based on this component gross weight in first kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

37. the composition of claim 35, wherein, the content of 2-phenyl isomer accounts for any amount of 57.00wt%～82.00wt% based on this component gross weight in first kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

38. the composition of claim 35, wherein, the content of 2-phenyl isomer accounts for any amount of 45.00wt%～82.00wt% based on this component gross weight in second kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

39. the composition of claim 35, wherein, the content of 2-phenyl isomer accounts for any amount of 57.00wt%～82.00wt% based on this component gross weight in second kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

40. the composition of claim 35, wherein, two kinds of components all are sulfonate, and wherein, described sulfonate all is to comprise the cationic salt that is selected from down group element: sodium, potassium, lithium, rubidium, magnesium, calcium and strontium.

41. the composition of claim 35, wherein, described mixture at room temperature is a solid, and it does not have fusing point in about 40 ℃～80 ℃ scopes by ASTM method D-3417 mensuration by dsc.

42. the composition of claim 40, wherein, described mixture neutralizes corresponding to the azochlorosulfonate acid mixture of described sulfonate in the aqueous solution from oxide compound, oxyhydroxide or the carbonate that utilization is selected from the metal of sodium, potassium, lithium, rubidium, magnesium, calcium and strontium.

43. the composition of claim 35, wherein, exist in first kind of component of described mixture based on first kind of component gross weight R in the sulfonate of 25wt% at least ₃It is methyl.

44. the composition of claim 35, wherein, exist in second kind of component of described mixture based on second kind of component gross weight R in the sulfonate of 25wt% at least ₃It is methyl.

45. the composition of claim 35, wherein, exist in first kind of component based on first kind of component gross weight R in the sulfonate of 50wt% at least ₃Be selected from sulfonic group or sulphonate-base.

46. the composition of claim 35, wherein, exist in second kind of component based on second kind of component gross weight R in the sulfonate of 50wt% at least ₃Be selected from sulfonic group or sulphonate-base.

47. aqueous solution that comprises the composition of claim 35, wherein, the merging amount of described first kind of component and described second kind of component is 0.09wt%～0.11wt% based on this total solution weight, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 200 NTU units is provided in the described aqueous solution.

48. aqueous solution that comprises the composition of claim 35, wherein, the merging amount of described first kind of component and described second kind of component is 0.09wt%～0.11wt% based on this total solution weight, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 150 NTU units is provided in the described aqueous solution.

49. aqueous solution that comprises the composition of claim 35, wherein, the merging amount of described first kind of component and described second kind of component is 0.09wt%～0.11wt% based on this total solution weight, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 50 NTU units is provided in the described aqueous solution.

50. composition of matter that is applicable to cleaning, it comprises the composition and at least a known preparation soap that is applicable to of claim 35, other component of washing composition etc., wherein, improvement comprises, in described first kind of component of described mixture and described second kind of component, provide effective 2-phenyl isomer content, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 200 NTU units, and wherein, the total sulfosalt surfactant concentration in the described composition is 0.09～0.11% any amount.

51. composition of matter that is applicable to cleaning, it comprises the composition and at least a known preparation soap that is applicable to of claim 35, other component of washing composition etc., wherein, improvement comprises, in described first kind of component of described mixture and described second kind of component, provide effective 2-phenyl isomer content, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 150 NTU units, and wherein, the total sulfosalt surfactant concentration in the described composition is 0.09～0.11% any amount.

52. composition of matter that is applicable to cleaning, it comprises the composition and at least a known preparation soap that is applicable to of claim 35, other component of washing composition etc., wherein, improvement comprises, in described first kind of component of described mixture and described second kind of component, provide effective 2-phenyl isomer content, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 50 NTU units, and wherein, the total sulfosalt surfactant concentration in the described composition is 0.09～0.11% any amount.

53. the composition of claim 35, wherein, the alkyl on described first kind of component is a linear alkyl.

54. the composition of claim 35, wherein, the alkyl on described first kind of component is a branched-alkyl.

55. the composition of claim 35, wherein, the alkyl on described second kind of component is a linear alkyl.

56. the composition of claim 35, wherein, the alkyl on described second kind of component is a branched-alkyl.

57. the composition of claim 35, it further comprises the known preparation soap that is applicable to, the other material of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, water-soluble branched-alkyl benzene sulfonate, ether sulfate, alkyl phenolic alkoxy thing, fatty acid amide, alhpa olefin sulfonate, paraffin sulfonate, betaine, sequestrant, the tallow amine ethoxylate, polyetheramine ethoxylate, ethylene oxide/propylene oxide segmented copolymer, fatty alcohol ethylene epoxide/propylene oxide low-foaming surfactant, methyl ester sulfonate, alkyl polysaccharide, N-methyl glucose amide, alkylation sulfonation phenyl ether, polyoxyethylene glycol, the 2-phenyl isomer content is less than 30.00% water-soluble alkyl toluene sulfonate, and the 2-phenyl isomer content is less than 26.00% water-soluble alkylbenzene sulfonate.

58. the composition of claim 57, wherein, the total concn of water-soluble sulfonate is 0.025wt%～25.00wt% based on total solution weight, and described concentration comprises one of each percentage between two numerical value percentage ratio.

59. the composition of claim 57, wherein, described other material total concn is 0.10wt%～25.00wt% based on total solution weight, and described concentration comprises one of each percentage between two numerical value percentage ratio.

60. the composition of claim 57, it further comprises the third component, wherein, described the third component is different from described second kind of component and is selected from down the group material: at least a known preparation soap that is applicable to, other component of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, water-soluble branched-alkyl benzene sulfonate, the 2-phenyl isomer content is less than 30.00% water-soluble alkyl toluene sulfonate, and the 2-phenyl isomer content is less than 26.00% water-soluble alkylbenzene sulfonate.

61. a solid bar shaped soap, the gross weight that it comprises based on this bar shaped soap is the composition of the claim 35 of 2.00wt%～25.00wt%.

62. mobile powdery de-sludging goods, it comprises composition and at least a known other component that is applicable to preparation soap, washing composition etc. of claim 35.

63. one kind is applicable to the solid piece of cleaning clothes, it comprises composition and at least a known other component that is applicable to preparation soap, washing composition etc. of claim 35.

64. one kind is applicable to that preparation is used for the composition of de-sludging composition finished product of clean textile, dish, crust and other base material, it is made of following component:

A) the first kind of component that exists with any amount based on mixture total weight amount 99.75wt%～0.25wt%, described first kind of component is characterised in that, it comprises the mixture of two or more water-soluble sulfonates, and this mixture comprises the 2-phenyl isomer of the sulfonated aromatic alkylide of being represented by following general formula based on any amount of this mixture total weight amount 30.00wt%～82.00wt%:

Wherein, n can equal 4～16 arbitrary integer, wherein, and R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be selected from sulfonic group or sulphonate-base, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be the substituting group that is selected from methyl and ethyl, described content comprises one of each percentage between two numerical value percentage ratio;

And

B) the second kind of component that exists with any amount based on mixture total weight amount 0.25%～99.75%, described second kind of component be characterised in that, it comprises the water-soluble sulfonate of the 2-phenyl isomer of the alkylbenzene of being represented by following general formula based on any amount of described second kind of component gross weight 50.00wt%～1.00wt%:

Wherein, the arbitrary integer that n equals 4～16, wherein, R ₁, R ₂, R ₃, R ₄And R ₅In any but have only one to be selected from sulfonic group or sulphonate-base, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In be not that those of sulfonic group or sulphonate-base all are hydrogen, described content comprises one of each percentage between two numerical value percentage ratio.

65. the composition of claim 64, wherein, the content of 2-phenyl isomer accounts for any amount of 45.00wt%～82.00wt% based on this component gross weight in first kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

66. the composition of claim 64, wherein, the content of 2-phenyl isomer accounts for any amount of 57.00wt%～82.00wt% based on this component gross weight in first kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

67. the composition of claim 64, wherein, the content of 2-phenyl isomer accounts for any amount of 45.00wt%～82.00wt% based on this component gross weight in second kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

68. the composition of claim 64, wherein, the content of 2-phenyl isomer accounts for any amount of 57.00wt%～82.00wt% based on this component gross weight in second kind of component, and described content comprises one of each percentage between two numerical value percentage ratio.

69. the composition of claim 64, wherein, two kinds of components all are sulfonate, and wherein, described sulfonate all is to comprise the cationic salt that is selected from down group element: sodium, potassium, lithium, rubidium, magnesium, calcium and strontium.

70. the composition of claim 64, wherein, described mixture at room temperature is a solid, and it has a fusing point in about 40 ℃～80 ℃ scopes by ASTM method D-3417 mensuration by dsc.

71. the composition of claim 69, wherein, described mixture neutralizes corresponding to the azochlorosulfonate acid mixture of described sulfonate in the aqueous solution from oxide compound, oxyhydroxide or the carbonate that utilization is selected from the metal of sodium, potassium, lithium, rubidium, magnesium, calcium and strontium.

72. the composition of claim 64, wherein, exist in first kind of component of described mixture based on first kind of component gross weight R in the sulfonate of 25wt% at least ₃It is methyl.

73. the composition of claim 64, wherein, exist in second kind of component of described mixture based on second kind of component gross weight R in the sulfonate of 25wt% at least ₃It is methyl.

74. the composition of claim 64, wherein, exist in first kind of component based on first kind of component gross weight R in the sulfonate of 50wt% at least ₃Be selected from sulfonic group or sulphonate-base.

75. the composition of claim 64, wherein, exist in second kind of component based on second kind of component gross weight R in the sulfonate of 50wt% at least ₃Be selected from sulfonic group or sulphonate-base.

76. aqueous solution that comprises the composition of claim 64, wherein, the merging amount of described first kind of component and described second kind of component is 0.09wt%～0.11wt% based on this total solution weight, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 200 NTU units is provided in the described aqueous solution.

77. aqueous solution that comprises the composition of claim 64, wherein, the merging amount of described first kind of component and described second kind of component is 0.09wt%～0.11wt% based on this total solution weight, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 150 NTU units is provided in the described aqueous solution.

78. aqueous solution that comprises the composition of claim 64, wherein, the merging amount of described first kind of component and described second kind of component is 0.09wt%～0.11wt% based on this total solution weight, and wherein, when the total hardness level of water was the arbitrary value of 100～300ppm, described component existed with significant quantity and the turbidity that is lower than 50 NTU units is provided in the described aqueous solution.

79. composition of matter that is applicable to cleaning, it comprises the composition and at least a known preparation soap that is applicable to of claim 64, other component of washing composition etc., wherein, improvement comprises, in described first kind of component of described mixture and described second kind of component, provide effective 2-phenyl isomer content, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 200 NTU units, and wherein, the total sulfosalt surfactant concentration in the described composition is 0.09～0.11% any amount.

80. composition of matter that is applicable to cleaning, it comprises the composition and at least a known preparation soap that is applicable to of claim 64, other component of washing composition etc., wherein, improvement comprises, in described first kind of component of described mixture and described second kind of component, provide effective 2-phenyl isomer content, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 150 NTU units, and wherein, the total sulfosalt surfactant concentration in the described composition is 0.09～0.11% any amount.

81. composition of matter that is applicable to cleaning, it comprises the composition and at least a known preparation soap that is applicable to of claim 64, other component of washing composition etc., wherein, improvement comprises, in described first kind of component of described mixture and described second kind of component, provide effective 2-phenyl isomer content, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 50 NTU units, and wherein, the total sulfosalt surfactant concentration in the described composition is 0.09～0.11% any amount.

82. the composition of claim 64, wherein, the alkyl on described first kind of component is a linear alkyl.

83. the composition of claim 64, wherein, the alkyl on described first kind of component is a branched-alkyl.

84. the composition of claim 64, wherein, the alkyl on described second kind of component is a linear alkyl.

85. the composition of claim 64, wherein, the alkyl on described second kind of component is a branched-alkyl.

86. the composition of claim 64, wherein, the any amount of the described first kind of component that exists in described first kind of described mixture of ingredients constitute and the 10.00wt%～55.00wt% of described second kind of component merging amount always, described content comprises one of each percentage between two numerical value percentage ratio.

87. the composition of claim 64, wherein, the any amount of the described first kind of component that exists in described first kind of described mixture of ingredients constitute and the 15.00wt%～48.00wt% of described second kind of component merging amount always, described content comprises one of each percentage between two numerical value percentage ratio.

88. the composition of claim 64, wherein, the any amount of the described first kind of component that exists in described first kind of described mixture of ingredients constitute and the 25.00wt%～35.00wt% of described second kind of component merging amount always, described content comprises one of each percentage between two numerical value percentage ratio.

89. the composition of claim 64, it further comprises the known preparation soap that is applicable to, the other material of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, water-soluble branched-alkyl benzene sulfonate, ether sulfate, alkyl phenolic alkoxy thing, fatty acid amide, alhpa olefin sulfonate, paraffin sulfonate, betaine, sequestrant, the tallow amine ethoxylate, polyetheramine ethoxylate, ethylene oxide/propylene oxide segmented copolymer, fatty alcohol ethylene epoxide/propylene oxide low-foaming surfactant, methyl ester sulfonate, alkyl polysaccharide, N-methyl glucose amide, alkylation sulfonation phenyl ether, polyoxyethylene glycol, the 2-phenyl isomer content is greater than 30.00% water-soluble alkylbenzene sulfonate, and the 2-phenyl isomer content is less than 50.00% water-soluble alkyl toluene sulfonate.

90. the composition of claim 89, wherein, the total concn of water-soluble sulfonate is 0.025wt%～25.00wt% based on total solution weight, and described concentration comprises one of each percentage between two numerical value percentage ratio.

91. the composition of claim 89, wherein, described other material total concn is 0.10wt%～25.00wt% based on total solution weight, and described concentration comprises one of each percentage between two numerical value percentage ratio.

92. the composition of claim 89, it further comprises the third component, wherein, described the third component is different from described second kind of component and is selected from down the group material: at least a known preparation soap that is applicable to, other component of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, water-soluble branched-alkyl benzene sulfonate, the 2-phenyl isomer content is less than 30.00% water-soluble alkyl toluene sulfonate, and the 2-phenyl isomer content is less than 26.00% water-soluble alkylbenzene sulfonate.

93. a solid bar shaped soap, it comprises the composition based on the claim 64 of the gross weight 2.00wt% of this bar shaped soap～25.00wt%.

94. mobile powdery de-sludging goods, it comprises composition and at least a known other component that is applicable to preparation soap, washing composition etc. of claim 64.

95. one kind is applicable to the solid piece of cleaning clothes, it comprises composition and at least a known other component that is applicable to preparation soap, washing composition etc. of claim 64.

96. composition that is applicable to the various surfaces of cleaning and other base material, it is made of following component: a) the alkyl toluene sulfonate surface active agent composition that exists with any amount based on finished product de-sludging composition total weight 0.25wt%～99.50wt%, described component is characterised in that, it comprises the water-soluble sulfonate of the 2-phenyl isomer of the alkyl toluene of being represented by following general formula based on any amount of this component gross weight 26.00wt%～82.00wt%:

Wherein, the arbitrary integer that n equals 4～16, wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be sulphonate-base, and wherein, R ₁, R ₂, R ₃, R ₄And R ₅In one and have only one to be the substituting group that is selected from methyl and ethyl, described content comprises one of two each percentages between numerical value percentage ratio;

And

B) at least a known preparation soap that is applicable to of 0.50%～99.75% any amount, other component of washing composition etc., wherein, at least a group material that is selected from down of described other component: lipid acid, alkyl-sulphate, thanomin, amine oxide, alkaline carbonate, water, ethanol, Virahol, pine tar, sodium-chlor, water glass, polymkeric substance, alcohol alkoxylate, zeolite, perborate, alkali metal sulfates, enzyme, hydrotropic agent, dyestuff, spices, sanitas, whitening agent, washing assistant, polyacrylate, essential oil, alkali metal hydroxide, ether sulfate, alkylphenol ethoxylate, fatty acid amide, alhpa olefin sulfonate, paraffin sulfonate, betaine, sequestrant, the tallow amine ethoxylate, polyetheramine ethoxylate, ethylene oxide/propylene oxide segmented copolymer, fatty alcohol ethylene epoxide/propylene oxide low-foaming surfactant, methyl ester sulfonate, alkyl polysaccharide, N-methyl glucose amide, alkylation sulfonation phenyl ether, the 2-phenyl isomer content is less than 26.00% water-soluble alkylbenzene sulfonate, and the 2-phenyl isomer content is greater than 26.00% water-soluble alkylbenzene sulfonate, and perhaps the 2-phenyl isomer content is less than 26.00% alkyl toluene sulfonate.

97. composition of matter that is applicable to cleaning, it comprises: alkyl toluene sulfonate anionic group and at least a known preparation soap that is applicable to, other component of washing composition etc., wherein, improvement comprises, the 2-phenyl isomer content of increase is provided in the alkyl toluene sulfonate anionic group, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 200NTU unit, and wherein, the surfactant concentration in the described cleaning soln is 0.09～0.11% any amount.

98. composition of matter that is applicable to cleaning, it comprises: alkyl toluene sulfonate anionic group and at least a known preparation soap that is applicable to, other component of washing composition etc., wherein, improvement comprises, the 2-phenyl isomer content of increase is provided in the alkyl toluene sulfonate anionic group, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 100NTU unit, and wherein, the surfactant concentration in the described cleaning soln is 0.09～0.11% any amount.

99. composition of matter that is applicable to cleaning, it comprises: alkyl toluene sulfonate anionic group and at least a known preparation soap that is applicable to, other component of washing composition etc., wherein, improvement comprises, the 2-phenyl isomer content of increase is provided in the alkyl toluene sulfonate anionic group, when the total hardness level of water is the arbitrary value of 100～300ppm, described content is enough to cause by mixing aqueous solution turbidity that described composition and tap water form less than 50 NTU units, and wherein, the surfactant concentration in the described cleaning soln is 0.09～0.11% any amount.

100. the composition of claim 96, wherein, described surface is selected from down the group material: fabric, dish, aluminium motor vehicle, dairy products equipment and aircraft.

101. a composition that is applicable to cleaning, wherein, described composition comprises based on said composition gross weight claim 1,58,64 or 94 each the compositions of 0.50wt% at least.

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