CN103044291A - Technique for preparation of alkyl diarene sulfonate - Google Patents
Technique for preparation of alkyl diarene sulfonate Download PDFInfo
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- CN103044291A CN103044291A CN2013100122377A CN201310012237A CN103044291A CN 103044291 A CN103044291 A CN 103044291A CN 2013100122377 A CN2013100122377 A CN 2013100122377A CN 201310012237 A CN201310012237 A CN 201310012237A CN 103044291 A CN103044291 A CN 103044291A
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Abstract
The invention discloses a technique for preparation of alkyl diarene sulfonate, and the technique comprises the following steps of: adding a catalyst, diarene and fatty alcohol in a reactor; thermally leaching the reactant liquid after reaction, decompressing and distilling the filtrate to obtain a mixture consisting of monoalkyl diarene and dialkyl diarene; decompressing and distilling the filtrate again at high temperature and high vacuum degree to obtain monoalkyl diarene; adding alkane in the monoalkyl diarene or in the mixture consisting of monoalkyl diarene and dialkyl diarene, and adding fuming sulphuric acid for reaction when the temperature is increased to 30-50 DEG C by heating; then adding water solution of alkaline to neutralize the solution until pH is 6-8; removing the solvent by means of vaporization to obtain alkyl diarene mono-sulfonate; adding a solvent in the monoalkyl diarene or in the mixture consisting of monoalkyl diarene and dialkyl diarene, adding a sulfonating agent for reaction after the temperature is increased to 30-80 DEG C by heating, and then adding water solution of alkaline to neutralize the solution until pH is 6-8; and at last removing the solvent by means of vaporization to obtain a mixture of alkyl diarene mono-sulfonate and alkyl diarene disulfonate or alkyl diarene disulfonate. The technique disclosed by the invention has the advantages of being simple and convenient, easy to realize industrialization and safe to people and environment.
Description
Technical field
The invention belongs to a kind of technique for preparing sulfonate, relate in particular to a kind of technique for preparing alkyl two arene sulfonates with Fatty Alcohol(C12-C14 and C12-C18) and two aromatic hydrocarbons.
Background technology
The most frequently used tensio-active agent of tertiary oil recovery mainly is sulfonated petro-leum and heavy alkylbenzene sulfonate at present, the two is complicated mixture, product forms the impact that is subject to the factors such as raw material sources, technique, stability is poor, and temperature resistant antisalt is poor, can improve salt tolerance after composite with nonionogenic tenside, but combination flooding chromatographic separation phenomenon is serious, causes oil displacement efficiency to descend.Therefore, need exploitation to be applicable to the sulfonate type anion surfactant of the novel texture of tertiary oil recovery.
Alkyl two arene sulfonates generally are to carry out alkylated reaction synthesis of alkyl two aromatic hydrocarbons by the alkylating agent such as halohydrocarbon or alkene, Fatty Alcohol(C12-C14 and C12-C18) and two aromatic hydrocarbons, carry out sulfonation with sulphonating agent again, the sulfonate type anion surfactant that obtains with the alkali neutralization afterwards.Wherein, alkylating agent and of crucial importance with the selection of catalyzer during preparation alkyl two aromatic hydrocarbons intermediate, this is the principal element that affects alkyl two arene sulfonate surfactant product quality and costs.Pertinent literature report mainly contains: 1. take alpha-olefin as alkylating agent and ditane at anhydrous AlCl
3Obtain two alkyl diphenyl methane under the catalysis, again with the chlorsulfonic acid reaction obtain two alkyl diphenyl methane disulfonates (in great waves, Hu Longjiang etc., Daqing Petroleum Institute's journal, 2004,28 (1): 35-38); 2. by 1-haloalkane and 1,2-diphenylethane at anhydrous AlCl
3Obtain alkyl diphenyl ethane under the catalysis, carry out sulfonation with oleum again and obtain two alkyl diphenyl ethane sulfonates (Cui Yingjun, Hebei University of Technology's Master's thesis, 2007).In addition; under catalyst action, carry out first acylation reaction by long-chain fat acyl chlorides and two aromatic hydrocarbons and generate two acyl group ditanes; become two alkyl two aromatic hydrocarbons through Clemmensen reduction; can make two straight chained alkyl two aromatic hydrocarbons disulfonate Gemini tensio-active agents through sulfonation, neutralization again; but this technique is too complicated; be difficult for realizing industrialization, do not belong to the scope that the present invention inquires into.
There is following problem among the existing alkyl two arene sulfonate preparation technologies:
When (1) adopting halohydrocarbon to be raw material synthesis of alkyl two aromatic hydrocarbons, can produce HCl in process of production, to the human and environment poor stability, serious to equipment corrosion.
When (2) adopting alkene to be raw material synthesis of alkyl two aromatic hydrocarbons, alkene derives from non-renewable petroleum resources, do not meet the fundamental state policy of green, recycling economy, moreover at present domestic alkene is mainly by external import, and price is high, originate limited, therefore, consider from the angle of national energy security, alkene is unsuitable for the main raw material as tertiary oil recovery.
(3) catalyzer commonly used mainly is an acidic catalysts such as the vitriol oil, hydrofluoric acid and aluminum chloride in the alkylated reaction, and is serious to the harm of environment, is difficult for and raw material and product separation etching apparatus.
(4) with haloalkane, when alpha-olefin is made alkylating agent, product composition is complicated, polysubstituted thing content and polymer content are higher in the alkylate, need distill out under the high temperature high vacuum monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons, energy consumption is high, facility investment is large.
Summary of the invention
The purpose of this invention is to provide a kind of simple process, be easy to realize industrialization, to people and environmental safety, the technique of preparation alkyl two arene sulfonates that energy consumption is low.
The present invention is a kind of technique for preparing alkyl two arene sulfonates, and concrete operation step is as follows:
(1) in reactor, adds catalyzer, two aromatic hydrocarbons, Fatty Alcohol(C12-C14 and C12-C18), catalyst levels is 5%～50% of Fatty Alcohol(C12-C14 and C12-C18) and two aromatic hydrocarbons total masses, the mol ratio of two aromatic hydrocarbons and Fatty Alcohol(C12-C14 and C12-C18) is 0.2～5:1, behind 100 ℃～200 ℃ reaction 10～200min, hot suction filtration reaction solution, filtrate is carried out underpressure distillation to remove unreacted two aromatic hydrocarbons and Fatty Alcohol(C12-C14 and C12-C18), bottoms is the mixture that monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form, this intermediate product can be directly used in sulfonation, also can carry out carrying out sulfonation after underpressure distillation obtains monoalkyl two aromatic hydrocarbons to bottoms under the high temperature condition of high vacuum degree again;
(2) mixture that adding monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form in reactor or monoalkyl two aromatic hydrocarbons, alkane, start and stir, add oleum when being heated to 30 ℃～50 ℃, the mixture that oleum and monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form or the mol ratio of monoalkyl two aromatic hydrocarbons are 1～1.1:1, reaction times 30～60min, the aqueous solution that adds again alkali is neutralized to PH 6～8, the mass concentration of the aqueous solution of alkali is 20～50%, boils off solvent and obtains alkyl two aromatic hydrocarbons monosulfonates;
(3) in reactor, add mixture or monoalkyl two aromatic hydrocarbons that monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form, solvent, start and stir, add sulphonating agent when being heated to 30 ℃～80 ℃, the mixture that sulphonating agent and monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form or the mol ratio of monoalkyl two aromatic hydrocarbons are 1.5～3.0:1, reaction times 30～90min, the aqueous solution that adds again alkali is neutralized to PH 6～8, the mass concentration of the aqueous solution of alkali is 20～50%, boils off mixture or alkyl two aromatic hydrocarbons disulfonates that solvent obtains alkyl two aromatic hydrocarbons monosulfonates and alkyl two aromatic hydrocarbons disulfonates.
Aforesaid Fatty Alcohol(C12-C14 and C12-C18) is R
3-OH, R
3Be C
8～C
18The straight or branched alkyl.
Aforesaid two aromatic hydrocarbons are Ar-X
1-Ar, X
1Be C
0～C
12The straight or branched alkyl, Ar is aromatic hydrocarbons, such as benzene or naphthalene.
Aforesaid catalyzer is one or more compositions in atlapulgite and sulfuric acid, tosic acid or the thionamic acid, and through the composite catalyst that floods, roasting obtains, wherein atlapulgite is Primary Catalysts, sulfuric acid, tosic acid or thionamic acid are promotor, and the consumption of promotor is 5～30% of Primary Catalysts quality.
The concrete preparation method of aforesaid composite catalyst is: the aqueous solution of atlapulgite and promotor is at room temperature stirred 6～24h, and suction filtration, filter cake is dried to constant weight under 150～300 ℃, with dried filter cake porphyrize, namely obtain composite catalyst.
The mass concentration of the aqueous solution of aforesaid promotor is not restricted, and can regulate amount of water, atlapulgite is all soaked and the liquid level of the aqueous solution is higher than atlapulgite and gets final product.
Aforesaid to filtrate carry out underpressure distillation take the actual conditions of removing unreacting material as: to the filtrate distilled that reduces pressure, steam≤200 ℃ front-end volatiles under 1～2.5 Kpa pressure, this cut can add to and carry out reuse in the reactor.
Aforesaid actual conditions under the high temperature condition of high vacuum degree bottoms being carried out underpressure distillation and obtain monoalkyl two aromatic hydrocarbons is: to the bottoms distilled that reduces pressure, collect 250 ~ 290 ℃ cut under 0.1～0.5 Kpa pressure.
Aforesaid alkane is C
6～C
20Alkane comprises normal paraffin, isoparaffin, branched paraffin, naphthenic hydrocarbon etc.
Aforesaid solvent is halohydrocarbon, comprises methylene dichloride, ethylene dichloride, trichloromethane etc.
Aforesaid sulphonating agent can be oleum, sulfan or gas sulphur trioxide.
Aforesaid alkali is the organic basess such as the mineral alkalis such as sodium hydroxide, potassium hydroxide, ammonium hydroxide (ammoniacal liquor) and monoethanolamine, diethanolamine, trolamine.
The skeleton symbol of alkyl two arene sulfonates of the present invention's preparation is as follows:
R wherein
1Be C
8～C
18The straight or branched alkyl, R
2Be H or and R
1Identical alkyl, M are sodium, potassium, ammonium, monoethanolamine, diethanolamine, trolamine positively charged ion.
Compare with existing preparation alkyl two arene sulfonate techniques, the present invention prepares alkyl two aryl sulfonate techniques and has the following advantages:
(1) preparation alkyl two arene sulfonate techniques of the present invention are take Fatty Alcohol(C12-C14 and C12-C18) as alkylating reagent, raw material sources are in reproducible natural fats and oils, alkylate is take monoalkyl two aromatic hydrocarbons as main, many alkyl substituent and polymer content are extremely low, do not need under the high temperature high vacuum, to distill out single, double alkyl two aromatic hydrocarbons, energy consumption is low, and facility investment is little.
(2) adopt the composite catalyst for preparing with atlapulgite and promotor among the preparation technology of the present invention, cost is low, is easy to separate with reaction system, and aftertreatment is simple, safe to human and environment, not etching apparatus.
(3) product that obtains of preparation technology of the present invention can be the alkyl two arene sulfonate tensio-active agents of different alkyl length, different alkyl substitution value, different two sulphonation rates, product forms and performance can be adjusted according to the characteristics of different crude oils, adaptability to crude oil is good, is conducive to improve the recovery ratio that difference is driven piece crude oil.
Description of drawings
Fig. 1 is the electrospray ionization mass spectrum figure of embodiment 1 single dodecyl ditane disulfonic acid sodium
Fig. 2 is the electrospray ionization mass spectrum figure of embodiment 2 single dodecyl diphenylethane disulfonic acid potassium
Fig. 3 is the electrospray ionization mass spectrum figure of embodiment 3 single dodecyl biphenyl disulfonic acid ammoniums
Fig. 4 is the electrospray ionization mass spectrum figure of embodiment 4 single octyl group dinaphthylmethane sodium monosulfates and two octyl group dinaphthylmethane sodium monosulfates.
Embodiment
Embodiment 1:
Add the aqueous solution of atlapulgite and sulfuric acid in the reactor of thermometer, electric mixer, the consumption of sulfuric acid is 5% of atlapulgite quality, stirs 6h under the room temperature, suction filtration, filter cake directly is dried to constant weight under 300 ℃, with dried filter cake porphyrize, namely obtain composite catalyst.
Add lauryl alcohol, ditane, catalyzer in the reactor with thermometer, electric mixer, the mol ratio of ditane and lauryl alcohol is 5:1, and catalyst levels is 5% of lauryl alcohol and ditane total mass.Open and stir and heating, 200 ℃ of temperature of reaction, reaction times 10min, hot suction filtration reaction solution, under 1.8Kpa pressure to the filtrate distilled that reduces pressure, steam≤200 ℃ front-end volatiles remove unreacted ditane and lauryl alcohol, afterwards again under 0.2 Kpa pressure to the bottoms distilled that reduces pressure, the cut of collecting 250 ~ 260 ℃ obtains intermediate product list dodecyl ditane.
In with the reactor of thermometer, electric mixer, reflux condensing tube, add single dodecyl ditane and methylene chloride, open and drip sulfan, SO when being heated with stirring to 30 ℃
3With the mol ratio of single dodecyl ditane be 2.2:1, add rear continuation reaction 90min, sulfonated products is neutralized to PH 7 with the NaOH aqueous solution of 25wt%, steams solvent and obtains single dodecyl ditane disulfonic acid sodium, has confirmed the structure of product by the electrospray ionization mass spectrum (see figure 1).Among Fig. 1: m/z 517.22 [M-Na]
-, m/z 247.11 [M-2Na]
2-, M is the mole molecular mass 540 of single dodecyl ditane disulfonic acid sodium.
Embodiment 2:
The aqueous solution that in the reactor with thermometer, electric mixer, adds atlapulgite, tosic acid, the consumption of tosic acid is 30% of atlapulgite quality, stir 24h under the room temperature, suction filtration, filter cake directly is dried to constant weight under 200 ℃, with dried filter cake porphyrize, namely obtain composite catalyst.
In the reactor with thermometer, electric mixer, add lauryl alcohol, diphenylethane, catalyzer.The mol ratio of diphenylethane and lauryl alcohol is 3:1, and catalyst levels is 10% of raw material lauryl alcohol and diphenylethane total mass.Open and stir and heating, 160 ℃ of temperature of reaction, reaction times 70min after heat suction filtration reaction solution, under 1.5 Kpa pressure to the filtrate distilled that reduces pressure, steam≤200 ℃ front-end volatiles to be to remove unreacted diphenylethane and lauryl alcohol, afterwards again under 0.1 Kpa pressure to the bottoms distilled that reduces pressure, the cut of collecting 260 ~ 275 ℃ obtains intermediate product list dodecyl diphenylethane.
In with the reactor of thermometer, electric mixer, reflux condensing tube, add single dodecyl diphenylethane, after adding the trichloromethane dissolving, open and stir, drip sulfan when being heated to 40 ℃, the mol ratio of sulfan and single dodecyl diphenylethane is 3.0:1, add rear continuation reaction 60min, sulfonated products is neutralized to PH 7.5 with the KOH aqueous solution of 20wt%, steams solvent and obtains single dodecyl two styroyl disulfonic acid potassium.By electrospray ionization mass spectrum (see figure 2) analysis confirmation structure and the purity of product, among Fig. 2: m/z 547.3 [M-K]
-, m/z 254.2 [M-2K]
2-, m/z 509.3 [M-2K+H]
-, M is the mole molecular mass 586 of single dodecyl diphenylethane disulfonic acid potassium.
Embodiment 3:
The aqueous solution that in the reactor with thermometer, electric mixer, adds atlapulgite, sulfuric acid and thionamic acid, the consumption of sulfuric acid is 2% of atlapulgite quality, the consumption of thionamic acid is 10% of atlapulgite quality, stir 12h under the room temperature, suction filtration, filter cake directly is dried to constant weight under 150 ℃, with dried filter cake porphyrize, namely obtain composite catalyst.
In the reactor with thermometer, electric mixer, add lauryl alcohol, biphenyl, catalyzer.The mol ratio 2:1 of biphenyl and lauryl alcohol, catalyst levels are 20% of raw materials quality.Open and stir and heating, 180 ℃ of temperature of reaction, reaction times 80min after heat suction filtration reaction solution, under 2.0 Kpa pressure to the filtrate distilled that reduces pressure, steam≤200 ℃ front-end volatiles to be to remove unreacted biphenyl and lauryl alcohol, afterwards again under 0.5 Kpa pressure to the bottoms distilled that reduces pressure, the cut of collecting 280 ~ 290 ℃ obtains intermediate product list dodecyl biphenyl.
In with the reactor of thermometer, electric mixer, reflux condensing tube, add single dodecyl biphenyl, after adding the trichloromethane dissolving, unlatching passes into the gas sulphur trioxide when being heated with stirring to 35 ℃, the mol ratio of gas sulphur trioxide and single dodecyl biphenyl is 2.5:1, add rear continuation reaction 70min, sulfonated products is neutralized to PH 6 with the 25wt% ammonium hydroxide aqueous solution, steams solvent and obtains single dodecyl biphenyl disulfonic acid ammonium.By electrospray ionization mass spectrum (see figure 3) analysis confirmation structure and the purity of product, among Fig. 3: m/z 240.2 [M-2NH
4]
2-, M is the mole molecular mass 516 of single dodecyl biphenyl disulfonic acid ammonium.
Embodiment 4:
The aqueous solution that in the reactor with thermometer, electric mixer, adds atlapulgite, sulfuric acid and tosic acid, the quality of sulfuric acid is 5% of atlapulgite quality, the quality of tosic acid is 10% of atlapulgite quality, stir 10h under the room temperature, suction filtration, filter cake is dried to constant weight under 250 ℃, with dried filter cake porphyrize, namely obtain composite catalyst.
In the reactor with thermometer, electric mixer, reflux condensing tube, add 2-Ethylhexyl Alcohol, dinaphthylmethane (that is, two-1-naphthalene methane, CAS 607-50-1), catalyzer.The mol ratio of dinaphthylmethane and 2-Ethylhexyl Alcohol is 0.8:1, and catalyst levels is 15% of raw materials quality.Open and stir and heating, 100 ℃ of temperature of reaction, reaction times 120min after heat suction filtration reaction solution, under 1.2 Kpa pressure, to the filtrate distilled that reduces pressure, steam≤200 ℃ front-end volatiles obtain the intermediate product that is comprised of single octyl group dinaphthylmethane and two octyl group dinaphthylmethanes to remove unreacted raw material.
In the reactor with thermometer, electric mixer, reflux condensing tube, add intermediate product, after adding the hexanaphthene dissolving, when being heated with stirring to 30 ℃, unlatching drips oleum, the mol ratio of oleum and octyl group dinaphthylmethane is 1.1:1, add rear continuation reaction 40min, sulfonated products is neutralized to PH7.8 with the 30wt% aqueous sodium hydroxide solution, obtains the mixture that is comprised of single octyl group dinaphthylmethane sodium monosulfate and two octyl group dinaphthylmethane sodium monosulfate.By electrospray ionization mass spectrum (see figure 4) analysis confirmation structure and the purity of product, among Fig. 4: m/z 459.6 [M
1-Na]
-, M
1Be single octyl group dinaphthylmethane sodium monosulfate molecular weight 482.6; M/z 571.8 [M
2-Na]
-, M
2Be two octyl group dinaphthylmethane sodium monosulfate molecular weight 594.8.
Embodiment 5:
The aqueous solution that in the reactor with thermometer, electric mixer, adds atlapulgite, tosic acid and thionamic acid, the consumption of tosic acid is 10% of atlapulgite quality, the consumption of thionamic acid is 2% of atlapulgite, stir 20h under the room temperature, suction filtration, filter cake is dried to constant weight under 180 ℃, with dried filter cake porphyrize, namely obtain composite catalyst.
In the reactor with thermometer, electric mixer, add stearyl alcohol, 3,4-dimethyl-3,4 phenylbenzene hexane (CAS:10192-93-5 is hereinafter to be referred as the hexichol octane), catalyzer.The mol ratio of hexichol octane and stearyl alcohol is 1:1, and catalyst levels is 50% of raw materials quality.Open and stir and heating, about 120 ℃ of temperature of reaction, reaction times 30min, hot suction filtration reaction solution, under 1.0Kpa pressure to the filtrate distilled that reduces pressure, steam≤200 ℃ front-end volatiles to be to remove unreacted stearyl alcohol and hexichol octane, obtain the intermediate product (that is: octadecyl hexichol octane) that is comprised of single octadecyl hexichol octane and two octadecyl hexichol octanes.
In with the reactor of thermometer, electric mixer, reflux condensing tube, add octadecyl hexichol octane, after adding eicosane (CAS:112-95-8) dissolving, when being heated with stirring to 50 ℃, unlatching adds oleum, the mol ratio of oleum and octadecyl hexichol octane is 1.0:1, add rear continuation reaction 80min, sulfonated products is neutralized to PH 6.2 with the 50% monoethanolamine aqueous solution, steams solvent and obtains the mixture that is comprised of single octadecyl hexichol octane list sulfonic acid monoethanolamine salt, two octadecyl hexichol octane list sulfonic acid monoethanolamine salt.
Embodiment 6:
The aqueous solution that adds atlapulgite, sulfuric acid in the reactor with thermometer, electric mixer, the consumption of sulfuric acid are 15% of atlapulgite quality, stir 8h under the room temperature, suction filtration, filter cake is dried to constant weight under 300 ℃, with dried filter cake porphyrize, namely obtain composite catalyst.
In the reactor with thermometer, electric mixer, add nonyl alcohol, phenylbenzene dodecane (CAS No. 5368-74-1), catalyzer.The mol ratio of phenylbenzene dodecane and nonyl alcohol is 0.2:1, and catalyst levels is 25% of raw materials quality.Open and stir and heating, temperature of reaction is controlled at about 150 ℃, reaction times 200min after heat suction filtration reaction solution, under 2.5 Kpa pressure to the filtrate distilled that reduces pressure, steam≤150 ℃ front-end volatiles, to remove unreacted raw material, obtain the intermediate product (that is: nonyl hexichol dodecane) that is formed by single nonyl hexichol dodecane, two nonyl hexichol dodecane.
With thermometer, electric mixer, add intermediate product in the reactor of reflux condensing tube, after adding the ethylene dichloride dissolving, when being heated with stirring to 80 ℃, unlatching adds sulfan, the mol ratio of sulfan and nonyl hexichol dodecane is 1.5:1, add rear continuation reaction 30min, sulfonated products is neutralized to PH 6.5 with the 35% trolamine aqueous solution, steams solvent and obtains by single nonyl hexichol dodecane list sulfonic acid triethanolamine salt, single nonyl hexichol dodecane disulfonic acid triethanolamine salt, two nonyl hexichol dodecane list sulfonic acid triethanolamine salts, the mixture that two nonyl hexichol dodecane disulfonic acid triethanolamine salts form.
Claims (14)
1. a technique for preparing alkyl two arene sulfonates is characterized in that comprising the steps:
(1) in reactor, adds catalyzer, two aromatic hydrocarbons, Fatty Alcohol(C12-C14 and C12-C18), catalyst levels is 5%～50% of Fatty Alcohol(C12-C14 and C12-C18) and two aromatic hydrocarbons total masses, the mol ratio of two aromatic hydrocarbons and Fatty Alcohol(C12-C14 and C12-C18) is 0.2～5:1, behind 100 ℃～200 ℃ reaction 10～200min, hot suction filtration reaction solution, filtrate is carried out underpressure distillation to remove unreacted two aromatic hydrocarbons and Fatty Alcohol(C12-C14 and C12-C18), bottoms is the mixture that monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form, and under the high temperature condition of high vacuum degree bottoms is carried out underpressure distillation and obtains monoalkyl two aromatic hydrocarbons;
(2) mixture that adding monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form in reactor or monoalkyl two aromatic hydrocarbons, alkane, start and stir, add oleum when being heated to 30 ℃～50 ℃, the mixture that oleum and monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form or the mol ratio of monoalkyl two aromatic hydrocarbons are 1～1.1:1, reaction times 30～60min, the aqueous solution that adds again alkali is neutralized to PH 6～8, the mass concentration of the aqueous solution of alkali is 20～50%, boils off solvent and obtains alkyl two aromatic hydrocarbons monosulfonates;
(3) in reactor, add mixture or monoalkyl two aromatic hydrocarbons that monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form, solvent, start and stir, add sulphonating agent when being heated to 30 ℃～80 ℃, the mixture that sulphonating agent and monoalkyl two aromatic hydrocarbons and two alkyl two aromatic hydrocarbons form or the mol ratio of monoalkyl two aromatic hydrocarbons are 1.5～3.0:1, reaction times 30～90min, the aqueous solution that adds again alkali is neutralized to PH 6～8, the mass concentration of the aqueous solution of alkali is 20～50%, boils off mixture or alkyl two aromatic hydrocarbons disulfonates that solvent obtains alkyl two aromatic hydrocarbons monosulfonates and alkyl two aromatic hydrocarbons disulfonates.
2. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1 is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) is R
3-OH, R
3Be C
8～C
18The straight or branched alkyl.
3. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1 is characterized in that described two aromatic hydrocarbons are Ar-X
1-Ar, X
1Be C
0～C
12The straight or branched alkyl, Ar is aromatic hydrocarbons.
4. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 3 is characterized in that described aromatic hydrocarbons is benzene or naphthalene.
5. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1, it is characterized in that described catalyzer is one or more compositions in atlapulgite and sulfuric acid, tosic acid or the thionamic acid, and through the composite catalyst that floods, roasting obtains, wherein atlapulgite is Primary Catalysts, sulfuric acid, tosic acid or thionamic acid are promotor, and the consumption of promotor is 5～30% of Primary Catalysts quality.
6. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1, it is characterized in that described to filtrate carry out underpressure distillation take the actual conditions of removing unreacting material as: under 1～2.5 KPa pressure to the filtrate distilled that reduces pressure, steam≤200 ℃ front-end volatiles, this cut adds to and carries out reuse in the reactor.
7. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1, it is characterized in that described actual conditions under the high temperature condition of high vacuum degree bottoms being carried out underpressure distillation and obtain monoalkyl two aromatic hydrocarbons is: under 0.1～0.5 KPa pressure, to the bottoms distilled that reduces pressure, collect 250～290 ℃ cut.
8. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1 is characterized in that described alkane is C
6～C
20Alkane.
9. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 8 is characterized in that described C
6～C
20Alkane normal paraffin, isoparaffin, branched paraffin or naphthenic hydrocarbon.
10. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1 is characterized in that described solvent is halohydrocarbon.
11. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 10 is characterized in that described halohydrocarbon is methylene dichloride, ethylene dichloride or trichloromethane.
12. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 10 is characterized in that described sulphonating agent is oleum, sulfan or gas sulphur trioxide.
13. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 1 is characterized in that described alkali is mineral alkali or organic bases.
14. a kind of technique for preparing alkyl two arene sulfonates as claimed in claim 13 is characterized in that described mineral alkali is sodium hydroxide, potassium hydroxide or ammonium hydroxide, organic bases is monoethanolamine, diethanolamine or trolamine.
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| CN111072523A (en) * | 2020-01-06 | 2020-04-28 | 中国日用化学研究院有限公司 | Preparation process of composite sulfonic acid of alkylbenzene and 1, 1-phenyl-alkyl phenyl ethane or salt thereof |
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