CN1340491A - Process for alkylating benzene and olefin - Google Patents
Process for alkylating benzene and olefin Download PDFInfo
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- CN1340491A CN1340491A CN00122840A CN00122840A CN1340491A CN 1340491 A CN1340491 A CN 1340491A CN 00122840 A CN00122840 A CN 00122840A CN 00122840 A CN00122840 A CN 00122840A CN 1340491 A CN1340491 A CN 1340491A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A process for alkylating benzene and olefine features that under the existance of solid acid as catalyst and the akylation conditions, benzene and single-bond C2-C15 olefine take part in alkylating reaction. It features that the organic or inorganic compounds or their mixture containing heavy-current negative element (10-3000ppm) are used as part of its raw materials. Its advantage is high reaction selectivity.
Description
The present invention relates to the alkylation of a kind of benzene and alkene, particularly relate to a kind of benzene and C
2-C
15The alkylated reaction of singly-bound alkene in the presence of solid acid catalyst generates the method for corresponding alkylbenzene.
The alkylated reaction of benzene and alkene is the important process of production Organic Chemicals in the petrochemical complex industry.The isopropyl benzene that the alkylated reaction of benzene and propylene generates is a reaction raw materials of producing phenol and acetone.The ethylbenzene that the alkylated reaction of benzene and ethene generates is important Organic Chemicals.The long-chain alkyl benzene that the alkylated reaction of benzene and long-chain olefin generates is the important source material of producing washing composition and tensio-active agent.
The alkylation process of benzene and alkene has many patent reports:
United States Patent (USP) 4,731,497 have described the alkylation of benzene and α long-chain olefin, and catalyzer is the H-mordenite, and alkylation reaction condition is: temperature 20-200 ℃; Alhpa olefin is the alkene of 10-20 carbon atom; Benzene/alkene ratio is 10: 1~3: 1.
United States Patent (USP) 5,043,511 and 5,191,134 have described the alkylation reaction method of benzene and long-chain olefin, and catalyzer is IIA, IIIB, the mixture of IVB family polyvalent metal and clay or macropore crystalline molecular sieve material.Reaction conditions is: temperature is 80-450 ℃, and pressure is 0.25-40atm, and benzene/alkene ratio is 0.1: 1~50: 1.
United States Patent (USP) 5,196,574 and 5,344,997 have described the alkylation reaction method of the alkene of benzene and 6-20 carbon, and catalyzer is fluorizated silicon-aluminum.Reaction conditions is: temperature is 80-140 ℃, and pressure is 200-1000psig, and benzene/alkene is than being 5-30.
United States Patent (USP) 5,198,595 have described the method that ethylbenzene is produced in the benzene alkylation with ethylene reaction, and catalyzer is an acidic mordenites, and reaction conditions is: temperature is 100-300 ℃, and pressure is 10-200bar, benzene/alkene ratio is 1: 1~3: 1.
United States Patent (USP) 5,396,011 has described the method that isopropyl benzene is produced in the benzene alkylation with propylene reaction, and catalyzer is WO
2/ ZrO
2Solid super-strong acid.Reaction conditions is: temperature 100-300 ℃, and pressure 2000-4000KPa.
United States Patent (USP) 5,600,050 has described the preparation method of benzene alkylation with ethylene catalysts, with halogen-containing compound treatment beta-molecular sieve and carrier, obtains high performance alkylation catalyst.
United States Patent (USP) 4,891,458,4,427,786,4,564,719,4,538,014,4,538,016 and European patent 295,020A has described the preparation method of molecular sieve catalyst respectively.With HF, NaF, KF, LiF, BF
3, NH
4Fluorochemicals such as F are handled ZSM-5, β, USY equimolecular sieve, obtain highly active molecular sieve catalyst.
Japanese patent laid-open 5-25,062 has described the method for the benzene alkylation with propylene reaction that with the heteropolyacid is catalyzer, and reaction conditions is: 160 ℃ of temperature, pressure are 450KPa, and benzene/alkene ratio is 4.7: 1.
All do not relate in the above-mentioned prior art and in benzene and olefin alkylation reaction raw material, add the compound that contains the strong electronegativity element carries out alkylated reaction as reaction promoter technology among the present invention.
The purpose of this invention is to provide a kind of optionally alkylation reaction method of benzene and alkene of high alkylbenzene that has.
The present inventor is surprised to find that, if in alkylated reaction material benzene and/or alkene, add the organic or inorganic compound that contains the strong electronegativity element, or its mixture is as reaction promoter, and select proper reaction conditions to carry out alkylated reaction, can improve the selectivity of reaction, and can improve the yield of alkylate oil simultaneously, and prolong life of catalyst.We studies show that: add the auxiliary agent that contains the strong electronegativity element in reaction mass, when these auxiliary agents contact with the acid site of solid acid catalyst in alkylated reaction, can interact, its result has changed the original acid properties of solid acid catalyst significantly, particularly therefore strength of acid has changed the catalytic property of solid acid catalyst in benzene and olefin alkylation reaction significantly.
The alkylation reaction method of benzene provided by the present invention and alkene comprises benzene and C
2-C
15Singly-bound alkene reacts under alkylation reaction condition in the presence of a kind of solid acid catalyst, it is characterized in that in alkylated reaction benzene feedstock and/or alkene, gross weight with benzene and alkene is a benchmark, contain 5-5000ppm, preferred 10-3000ppm, more preferably the organic or inorganic compound that contains the strong electronegativity element or its mixture of 10-2000ppm.
Said C in the method provided by the invention
2-C
15Singly-bound alkene is ethene, propylene or laurylene-1 preferably.
Said strong electronegativity element halogen preferably in the method provided by the invention, the said organic or inorganic compound that contains the strong electronegativity element be hydrogen halide or can be decomposed into the inorganic or organic compound of hydrogen halide under alkylation conditions preferably.In general all inorganic or organic compound that can be decomposed into hydrogen halide under alkylation conditions may be used to the present invention, but preferred mineral compound is hydrogen halide such as HF, HCl, HBr and HI, is more preferably HF or HCl; Preferred organic compound is the halogen-containing organic compound with 2~8 carbon atoms.The said organic or inorganic compound that contains the strong electronegativity element also can be two or more the mixture in the above-claimed cpd.
Said organic compound includes, but not limited to have one or dihalogenated alkane of 2~8 carbon atoms, for example a fluoroethane in the method provided by the invention, monochlorethane, 1-fluoropropane, n-propyl chloride, 2-fluoropropane, 1-fluorine butane, 1-chlorobutane, 1-n-butyl bromide, 2-fluorine butane, 1,3-difluoro butane, 1,3-dichlorobutane, 1-fluorine iso-pentane, 1-fluorine hexane, 2-fluorine hexane, 1-fluorine heptane, n octyl fluoride, 2-fluoro-octane, 1-chloro-octane, fluoro octane-iso etc.
The said organic or inorganic compound that contains the strong electronegativity element is most preferred in the method provided by the invention is hydrogen fluoride or hydrogenchloride.
Said solid acid catalyst is the various solid acid catalysts that are used for the alkylated reaction of benzene and alkene in the prior art in the method provided by the invention, comprises heteropolyacid salt catalyst, the SO of carried heteropoly acid catalyst, load or not load
4 2-/ oxide compound super acidic catalyst, zeolite [molecular sieve, loading type Br nsted-Lewis (B-L) conjugation solid super acid catalyst and Br nsted acid or acid-treated oxide compound of Lewis or molecular sieve catalyst etc., the present invention has no particular limits it; But the solid acid catalyst that preferably contains the heteropllyacids material, for example disclosed loading type B-L conjugation solid super acid catalyst among disclosed carried heteropoly acid catalyst and the CN1246386A among the CN1232814A.
Said carried heteropoly acid catalyst is made up of porous inorganic carrier and a kind of heteropolyacid in the method provided by the invention, and wherein said heteropolyacid general formula is H
8-n[AM
12O
40], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5; Said porous inorganic carrier is conventional porous inorganic carrier, comprise aluminosilicate zeolite, carbon fiber, natural clay of gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic etc., or their mixture, wherein preferably silicon oxide, aluminum oxide or their mixture; This catalyzer is existing the description in CN1232814A, this with the document as reference of the present invention.The heteropolyacid salt catalyst of said load or not load and above-mentioned catalyzer are similar in the method provided by the invention, and different is the alkali metal salts or ammonium salt that wherein said heteropolyacid salt is above-mentioned heteropolyacid.
Said loading type Br nsted-Lewis conjugation solid super acid catalyst such as CN1246467A describe in the method provided by the invention, this with the document as reference of the present invention; Wherein preferably formed by a kind of heteropolyacid of a kind of porous inorganic carrier of the heavy % of 40-95 and the load heavy % of 1-60 on it and a kind of Lewis acid of the heavy % of 0.3-15; The definition of wherein said heteropolyacid and porous inorganic carrier is identical with top definition to heteropolyacid and porous inorganic carrier; Said Lewis acid is selected from AlCl
3, BF
3Perhaps XF
5, wherein X is P, As, Sb or Bi.This catalyzer is existing the description in CN1246467A, this with the document as reference of the present invention.
Other catalyzer described in the method provided by the invention all are corresponding catalyst of the alkylated reaction that is used for benzene and alkene of disclosed routine in the prior art, and the present invention has no particular limits it.
The condition of said alkylated reaction changes according to the carbon chain lengths of alkene and the difference of catalyst system therefor in the method provided by the invention, can be the reaction conditions that generally adopts in the prior art, and the present invention has no particular limits it; For example, temperature of reaction can be 40-350 ℃; Reaction pressure can be 0.5-10MPa; The scope of benzene and olefin molar ratio is 1.0-20, preferred 2.0-10.
The alkylation of benzene provided by the invention and alkene can carry out in various reactors, as fixed-bed reactor, intermittently tank reactor, moving-burden bed reactor, liquefied bed reactor or three-phase slurry bed reactor.The flow pattern of material can be that upstriker also can be a downstriker.
The alkylation of benzene provided by the invention and alkene is owing to add the auxiliary agent that contains the strong electronegativity element in reaction raw materials, when reaction raw materials contacts with solid acid catalyst in alkylated reaction, containing the auxiliary agent of strong electronegativity element and the acid active centre of catalyzer interacts, improved the original acid properties of solid acid catalyst, as strength of acid, acid distribution and acid site density etc.; Consequently change the catalytic performance of solid acid catalyst in alkylated reaction, made the selectivity of alkylated reaction obviously improve.
The alkylated reaction of said benzene of the present invention and alkene intermittently carries out in the still reaction system at a cover.Analytical procedure: adopt the composition of SP-3420 chromatogram on-line analysis gas-phase product, chromatographic column is the OV-01 kapillary crosslinking column of 50m * 0.2mm, with the full composition of HP-5890 (hewlette-packard product) stratographic analysis alkylate oil.Chromatographic column is the OV-01 capillary column of 50m * 0.2mm.
By direct elaboration in this full disclosure the present invention, the following examples will be further described specifically the present invention, but they can not be interpreted as the qualification to protection domain of the present invention.
Embodiment 1
Carry out the alkylated reaction of benzene and propylene according to method provided by the invention.
Take by weighing 5.24g phospho-wolframic acid (H
3PW
12O
40.22H
2O, analytical pure, the Beijing Chemical Plant produces) be dissolved in the 35ml deionized water, be made into H
3PW
12O
40The aqueous solution.With the 18.5g granularity is 40-60 purpose silica gel (SiO
2, Haiyang Chemical Plant, Qingdao produces) and put into filter flask, handled 1.0 hours down 0.095 MPa vacuum tightness and 75 ℃, cool to room temperature, under the condition that keeps vacuum, add the H for preparing
3PW
12O
40Solution flooded 1.0 hours, then 100 ℃ of vacuum-dryings 4 hours, obtained containing 20 heavy %H
3PW
12O
40Carried heteropoly acid catalyst with 80 heavy % silica gel is designated as 20%H
3PW
12O
40/ SiO
2, the specific surface of catalyzer is 380m
2/ g.The specific surface of catalyzer adopts cryogenic nitrogen absorption BET method to measure.The preparation method of other carried heteropoly acid catalyst is same as described above.
The alkylation of carrying out benzene and propylene in autoclave generates the reaction of isopropyl benzene, adds the above-mentioned carried phospho-tungstic acid catalyzer of 3.0g (20%H in reactor
3PW
12O
40/ SiO
2), add the benzene (analytical pure, the Beijing Chemical Plant produces) that 50.0g contains 150ppm HF then, under the strong mixing, be warmed up to 60 ℃, feed the 8.94g propylene, react under the violent stirring, react after 60 minutes, stop to stir.Amount to be cooled after room temperature, that release is emitted propylene and measured unreacted propylene with accurate under meter, the composition of chromatographically reaction product, reaction result is listed in the table 1.
Propylene conversion is defined as the per-cent of total mole number of the propylene of the mole number of the propylene that is converted into product and adding, the mole number of the isopropyl benzene in the product that the definition of isopropyl benzene selectivity is made a living and the per-cent of the total mole number that generates product in the table 1.
Comparative Examples 1
Repeat the alkylated reaction step of embodiment 1, different is not contain any compound of strong electrolyte element that contains as reaction promoter in raw material for alkylation benzene or propylene.The results are shown in Table 1 in reaction.
Embodiment 2
Repeat the alkylated reaction step of embodiment 1, different is to contain the HF of 1500ppm as reaction promoter in the benzene that adds.The results are shown in Table 1 in reaction.
Embodiment 3
Repeat the alkylated reaction step of embodiment 1, different is to contain organic fluoride-butyl fluoride of 500ppm as reaction promoter in the benzene that adds.The results are shown in Table 1 in reaction.
Embodiment 4
Repeat the alkylated reaction step of embodiment 1, the HF that different is contains 250ppm in the benzene that adds is as reaction promoter, and temperature of reaction is 40 ℃.The results are shown in Table 1 in reaction.
Embodiment 5
Repeat the alkylated reaction step of embodiment 4, different is that temperature of reaction is 200 ℃.The results are shown in Table 1 in reaction.
Embodiment 6
With 10.0g load type silicotungstic acid catalyst (20%H
4SiW
12O
40/ SiO
2, the preparation method is with embodiment 1, and just raw material changes silicotungstic acid H into
4SiW
12O
40.22H
2O (Beijing Chemical Plant)) carries out the alkylated reaction of benzene and propylene in the reactor of packing into, identical among reaction mass, reaction conditions and process and the embodiment 1, the n octyl fluoride that contains 800ppm in the benzene that different is adds is as reaction promoter, and reaction result is listed in the table 1.
Comparative Examples 2
Repeat the alkylated reaction step of embodiment 6, different is not contain any compound of strong electrolyte element that contains as reaction promoter in raw material for alkylation benzene or propylene.The results are shown in Table 1 in reaction.
Embodiment 7
Present embodiment illustrates with a kind of heteropolyacid salt catalyst (C
S2.5H
0.5PW
12O
40) carry out the alkylated reaction of benzene and propylene.
With 22.81gH
3PW
12O
40.21H
2O phospho-wolframic acid (chemical reagent factory of Beijing Xinhua product, analytical pure) and 2.85gC
S2CO
3(northern Tonghua factory products, analytical pure) is made into the solution of 0.35 and 0.87 volumetric molar concentration respectively, under violent stirring, with gained C
S2CO
3Solution slowly is added dropwise to H
3PW
12O
40In the solution, C
S2CO
3After solution dropwises, continue to stir 30 minutes, then with the white precipitate that obtains 50 ℃ of dryings 24 hours, obtain C
S2.5H
0.5PW
12O
40.8H
2The O heteropolyacid salt.With the C for preparing
S2.5H
0.5PW
12O
40.8H
2O is levigate, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets 40~60 purpose particles as catalyzer.
The above-mentioned heteropolyacid salt catalyst of gained packed into carry out the alkylated reaction of benzene and propylene in the reactor, identical among reaction mass, reaction conditions and process and the embodiment 1, reaction result is listed in the table 1.
Comparative Examples 3
Repeat the alkylated reaction step of embodiment 7, different is not contain any compound of strong electrolyte element that contains as reaction promoter in raw material for alkylation benzene or propylene.The results are shown in Table 1 in reaction.
Embodiment 8
The solid acid alkylation catalysts that this embodiment uses is that (B:Br nsted acid is H to B-L conjugation super acids here
3PW
12O
40L:Lewis acid is SbF here
5) catalyzer.This Preparation of catalysts method is as follows: the method for pressing among the embodiment 1 prepares 20%H earlier
3PW
12O
40/ SiO
2Catalyzer is then with this 20%H of 10.0g
3PW
12O
40/ SiO
2Packing in the fixed-bed reactor, is 120 hours with air speed
-1Nitrogen gas stream handled 4 hours at 100 ℃, cool to 50 ℃ then, make nitrogen gas stream SbF is housed through one
5Storage bottle, carry SbF
5The above-mentioned catalyzer of flowing through, the time is 3.5 hours, makes SbF
5Obtain B-L acid with the heteropolyacid interaction, purged 1.0 hours with nitrogen gas stream at last, make H
3PW
12O
40-SbF
5/ SiO
2Catalyzer is used for alkylated reaction.
The above-mentioned B-L conjugation of gained super acidic catalyst packed into carry out the alkylated reaction of benzene and propylene in the reactor, identical among reaction mass, reaction conditions and process and the embodiment 1, different is that temperature of reaction is 50 ℃, and reaction result is listed in the table 1.
Embodiment 9
With 20.0 gram zirconyl chloride (ZrOCl
2.8H
2O, analytical pure, Beijing Chemical Plant) be dissolved in 180 ml waters, under room temperature and agitation condition,, be 10.5, stop dropping ammonia and stirring then until the pH of solution value to the ammonia soln that wherein slowly splashes into 25 weight %, aged at room temperature 24 hours, again with distilled water wash, be filtered to no Cl
-Ion, 100 ℃ of dryings 5 hours obtain Zr (OH)
4The sulphuric acid soln of preparation 1.0M is by 10 milliliters of these sulphuric acid solns/1 gram Zr (OH)
4Ratio with this 1.0M sulphuric acid soln dipping Zr (OH)
4Solid 4.0 hours filters out unnecessary acid solution, with 100 ℃ of dryings of gained solid 3 hours, 550 ℃ of roasts 4.0 hours, obtains SO then
4 =/ ZrO
2Solid super-strong acid.With the SO for preparing
4 =/ ZrO
2Solid super-strong acid is worn into fine powder, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets 20~40 purpose particles as catalyzer.
With the above-mentioned SO of gained
4 =/ ZrO
2Solid super acid catalyst is packed into and is carried out the alkylated reaction of benzene and propylene in the reactor, identical among reaction mass, reaction conditions and process and the embodiment 1, the HCl that contains 150ppm in the benzene that different is adds is as reaction promoter, and reaction result is listed in the table 1.
Comparative Examples 4
Repeat the alkylated reaction step of embodiment 9, different is not contain any compound of strong electrolyte element that contains as reaction promoter in raw material for alkylation benzene or propylene.The results are shown in Table 1 in reaction.
Table 1
Propylene conversion (mole %) | Isopropyl benzene selectivity (mole %) | |
Embodiment 1 | ????100 | ????93.8 |
Comparative Examples 1 | ????100 | ????84.7 |
Embodiment 2 | ????100 | ????95.7 |
Embodiment 3 | ????100 | ????94.6 |
Embodiment 4 | ????97.8 | ????94.1 |
Embodiment 5 | ????100 | ????90.7 |
Embodiment 6 | ????100 | ????93.1 |
Comparative Examples 2 | ????100 | ????85.1 |
Embodiment 7 | ????100 | ????96.3 |
Comparative Examples 3 | ????100 | ????84.1 |
Embodiment 8 | ????100 | ????95.4 |
Embodiment 9 | ????100 | ????94.0 |
Comparative Examples 4 | ????100 | ????83.1 |
Embodiment 10
Carry out the alkylated reaction of benzene and laurylene according to method provided by the invention.
The alkylation of carrying out benzene and laurylene in autoclave generates the reaction of dodecylbenzene.Carried phospho-tungstic acid catalyzer (the 20%H that in reactor, adds preparation among the 4.0g embodiment 1
3PW
12O
40/ SiO
2), add the benzene (analytical pure, the Beijing Chemical Plant produces) that 55.0g contains 450ppm HF then, be warmed up to 80 ℃ under stirring, add 29.6g laurylene-1, react under the violent stirring, react after 90 minutes stopped reaction.To be cooled to room temperature, the composition of chromatographically reaction product, and calculate laurylene-1 transformation efficiency and dodecyl benzene selective, reaction result is listed in the table 2.
The laurylene transformation efficiency is defined as the per-cent of total mole number of the laurylene-1 of the mole number of the laurylene-1 that is converted into product and adding, the mole number of the dodecylbenzene in the product that the definition of dodecylbenzene selectivity is made a living and the per-cent of the total mole number that generates product in the table 2.
Comparative Examples 5
Repeat the alkylated reaction step of embodiment 10, different is not contain any compound of strong electrolyte element that contains as reaction promoter in raw material for alkylation benzene or laurylene-1.The results are shown in Table 2 in reaction.
Embodiment 11
Repeat the alkylated reaction step of embodiment 10, different is the heteropolyacid salt catalyst of employed catalyzer for preparation among the embodiment 7.The results are shown in Table 2 in reaction.
Comparative Examples 6
Repeat the alkylated reaction step of embodiment 11, different is not contain any compound of strong electrolyte element that contains as reaction promoter in raw material for alkylation benzene or laurylene-1.The results are shown in Table 2 in reaction.
Table 2
Laurylene transformation efficiency (mole %) | Dodecyl benzene selective (mole %) | |
Embodiment 10 | ????100 | ????92.8 |
Comparative Examples 5 | ????100 | ????81.3 |
Embodiment 11 | ????100 | ????93.1 |
Comparative Examples 6 | ????100 | ????82.7 |
Claims (12)
1, the alkylation reaction method of a kind of benzene and alkene comprises benzene and C
2-C
15Singly-bound alkene reacts under alkylation reaction condition in the presence of a kind of solid acid catalyst, it is characterized in that in alkylated reaction benzene feedstock and/or alkene, gross weight with benzene and alkene is a benchmark, contains the organic or inorganic compound that contains the strong electronegativity element or its mixture of 10-3000ppm.
2, according to the process of claim 1 wherein that said strong electronegativity element is a halogen.
3, according to the process of claim 1 wherein that the said compound that contains the strong electronegativity element is hydrogen halide or the inorganic or organic compound that can be decomposed into hydrogen halide under alkylation conditions.
4, according to the method for claim 3, wherein said organic compound is one or a dihalogenated alkane with 2~8 carbon atoms.
5, according to the method for claim 1 or 3, the wherein said compound that contains the strong electronegativity element is hydrogen fluoride or hydrogenchloride.
6, according to the process of claim 1 wherein said C
2-C
15Singly-bound alkene is ethene, propylene or laurylene-1.
7, according to the process of claim 1 wherein that said alkylation reaction condition is temperature of reaction 20-350 ℃, reaction pressure is 0.5-10MPa, and the scope of benzene and olefin molar ratio is 1.0-20.
8, according to the process of claim 1 wherein that said solid acid catalyst is heteropolyacid salt catalyst, zeolite [molecular sieve, the SO of carried heteropoly acid catalyst, load or not load
4 2-/ oxide solid super acidic catalyst, loading type Br nsted-Lewis conjugation solid super acid catalyst or Br nsted acid or acid-treated oxide compound of Lewis or molecular sieve catalyst.
9, according to the method for claim 8, the heteropolyacid salt catalyst that wherein said solid acid catalyst is carried heteropoly acid catalyst, load or not load, loading type Br nsted-Lewis conjugation solid super acid catalyst.
10, according to the method for claim 8 or 9, wherein said carried heteropoly acid catalyst is made up of porous inorganic carrier and a kind of heteropolyacid, and wherein said heteropolyacid general formula is H
8-n[AM
12O
40], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5; Said porous inorganic carrier is the porous inorganic carrier of the aluminosilicate zeolite that comprises gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic, carbon fiber, natural clay etc., or their mixture.
11, according to the method for claim 10, wherein said porous inorganic carrier is silicon oxide, aluminum oxide or their mixture.
12, according to the method for claim 8 or 9, wherein said loading type Br nsted-Lewis conjugation solid super acid catalyst is made up of a kind of heteropolyacid of a kind of porous inorganic carrier of the heavy % of 40-95 and the load heavy % of 1-60 on it and a kind of Lewis acid of the heavy % of 0.3-15; Identical in the definition of wherein said heteropolyacid and porous inorganic carrier and the claim 11 to the definition of heteropolyacid and porous inorganic carrier; Said Lewis acid is selected from AlCl
3, BF
3Perhaps XF
5, wherein X is P, As, Sb or Bi.
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WO2005070854A1 (en) | 2004-01-19 | 2005-08-04 | China Petroleum & Chemical Corporation | Solid catalytic process for alylating aromatic hydrocarbon or isometric parafin and olefin |
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CN108217679B (en) * | 2016-12-09 | 2020-03-27 | 中国科学院大连化学物理研究所 | Mordenite molecular sieve, and preparation method and application thereof |
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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