CN1345708A - Method for preparing alkylbenzene by position rearrangement reaction of substituted alkyl on benzene ring - Google Patents

Abstract

The present invention relates to a preparation method of alkylenzene, and is characterized by the under the catalytic action of loaded or unloade heteropolyacid compound it makes C1-C10 alkylbenzenes produce position rearragement reaction of substituting alkyl on benzene ring at 120-300 deg.c to respectively obtain meta-alkylbenzene and homo-alkylbenzene. Said invention method possesses the following advantages: 1. it substitutes AlCl3 catalyst, eliminates the corrosion and pollution produced in the course of production can simplifies technological process; and 2. its reaction temp. is lower, it is favorable for inhibiting side reaction, and 3. the low-temp. activity of catalyst is high, its stability is good and its activation method is simple and convenient.

Description

The method for preparing alkylbenzene by position rearrangement reaction of substituted alkyl on benzene ring

The present invention relates to prepare the method for alkylbenzene, specifically is exactly by making the substituted alkyl position on the phenyl ring that the method that rearrangement reaction prepares its isomeric alkylbenzene take place.

Dialkyl benzene between the industrial rearrangement reaction preparation that utilizes this substituted alkyl on benzene ring usually, p dialkyl benzene and equal polyalkylbenzene etc., especially between the production of dialkyl benzene all the more so.Representational is a methyl-ethyl benzene, a cymene, NSC 62102 and a diisopropyl benzene etc.Between methyl-ethyl benzene and NSC 62102 generate by dehydrogenation between a methyl ethylene benzene and a Vinylstyrene, they all are important polymerization single polymerization monomers, Vinylstyrene and cinnamic interpolymer are mainly used to make high performance ion exchange resin in the middle of it; Between methyl ethylene benzene and styrene copolymerizedly can be used to produce high temperature resistant and the multipolymer of good fluidity is arranged, and the improving agent of phthalic resin coating.Between diisopropyl benzene, a cymene be used for producing diphenol and meta-cresol between the Fine Organic Chemical product of high added value respectively.Between diphenol and meta-cresol be mainly used to synthetic extraordinary resin, medicine, highly effective pesticide, softening agent, coating and oxidation inhibitor etc.

Between dialkyl benzene generally prepare through alkylated reaction by monoalkylated benzenes and monoolefine.Because the positioning action of substituted radical alkyl on the monoalkylated benzenes, in the dialkyl benzene product of generation, about 80% is ortho para, only the accounting for about 20% an of position.In order to improve the yield of a dialkyl benzene, industrial with AlCl ₃Be catalyzer, make the dialkyl benzene generation alkyl position rearrangement reaction reaction of ortho para be converted into a dialkyl benzene.With AlCl ₃For the advantage of catalyzer is that temperature of reaction and pressure are low, the selectivity height of a dialkyl benzene, but the catalyst consumption amount is big, and corrodibility is strong, and three waste discharge is many, contaminate environment.

In order to solve corrosion and the problem of environmental pollution in the production process, the application of solid acid catalyst in the position rearrangement reaction of substituted alkyl on benzene ring reaction obtained development quickly.Wherein the catalyzer of molecular sieve such as HZSM-12, mordenite (HM), β zeolite and HY are obtaining result preferably on the dialkyl benzene between preparation; But the selectivity and the AlCl that have temperature of reaction height, a dialkyl benzene ₃Technology differ the not high defective of depth of conversion of bigger and adjacent dialkyl benzene, products obtained therefrom is difficult to satisfy the requirement of existing dialkyl benzene deep processing technology.

The reaction of position rearrangement reaction of substituted alkyl on benzene ring is subjected to the chemical thermodynamics balancing control.Being converted into a dialkyl benzene with the dialkyl benzene of ortho para is example, and elevated temperature, ortho para dialkyl benzene content in equilibrium products can increase.Because adjacent dialkyl benzene causes adverse influence to the deep processing meeting of a dialkyl benzene, thus in the actual production usually the content to adjacent dialkyl benzene in the product strict regulation is arranged.Reduce the degree of depth conversion that temperature of reaction helps adjacent dialkyl benzene in theory, reduce its relative content in product.But in fact, reduce temperature of reaction and will prolong reaction arrival balance time on the one hand, also will weaken activity of such catalysts on the other hand, cause the transformation efficiency of ortho para dialkyl benzene to reduce.So improving the key of ortho para dialkyl benzene transformation efficiency is to improve activity of such catalysts, especially the low temperature active of catalyzer.

First purpose of the present invention provides a kind of under the katalysis of heteropllyacids compound, makes the substituted alkyl on benzene ring occurrence positions reset the method for position alkylbenzene between generation, solves corrosion and pollution problem that current technology exists.

Second purpose of the present invention provides a kind of under the katalysis of heteropllyacids compound, the substituted alkyl on benzene ring occurrence positions reset generated all methods of position alkylbenzene, solves corrosion and pollution problem that current technology exists.

The preparation method of provided by the invention position alkylbenzene comprises: in load or not under the katalysis of the heteropllyacids compound of load, make the C that contains dialkyl benzene ₁～C ₁₀Alkylbenzene is 120～300 ℃ of position rearrangement reaction reactions that substituted alkyl on benzene ring takes place down.

Specifically, be in load or not under the katalysis of the heteropllyacids compound of load, make the C that contains dialkyl benzene ₁～C ₁₀, preferred C ₁～C ₅Alkylbenzene is at 120～300 ℃, and preferred 130～250 ℃, more preferred 135～200 ℃ of position rearrangement reactions that substituted alkyl on benzene ring takes place down react.Reaction pressure can be the pressure that under normal pressure or a certain temperature of reaction reactant is in a liquid state, and generally is normal pressure～4.0MPa, preferred normal pressure～3.0MPa.In batch reactor, the weight ratio of charging and catalyzer can be any ratio, preferred 3～50: 1, and the reaction times generally is 0.5～5h, preferred 1～3h.In flow reactor, the feeding liquid hourly space velocity generally is 0.1～30h ^-1, preferred 0.5～20h ^-1

Said reaction raw materials can be the alkylate of monoalkylated benzenes and monoolefine, or the mixture of alkylate and dialkyl benzene; Also can be dialkyl benzene or two or more dialkyl benzene of arbitrary proportion blended of pure a certain structure.These raw materials can directly use, but industrially generally mix use with a certain amount of monoalkylated benzenes and trialkyl benzene, to reduce the generation of disproportionation reaction.The content of monoalkylated benzenes in charging can be 0～80%, preferred 20%～70%; The content of trialkyl benzene in charging can be 0～20%, preferred 5%～10%.The preferred toluene of said monoalkylated benzenes, ethylbenzene, isopropyl benzene and tert.-butylbenzene etc.Said dialkyl benzene is preferred adjacent, to first and second benzene of a, position, adjacent, to the cymene of a, position, adjacent, to the diethylbenzene of a, position and neighbour, to the diisopropylbenzene(DIPB) of a, position etc.

The preparation method of equal position provided by the invention alkylbenzene comprises: in load or not under the katalysis of the heteropllyacids compound of load, make the C that contains trialkyl benzene ₁～C ₁₀Alkylbenzene is 120～300 ℃ of position rearrangement reaction reactions that substituted alkyl on benzene ring takes place down.

Specifically, be in load or not under the katalysis of the heteropllyacids compound of load, make the C that contains trialkyl benzene ₁～C ₁₀, preferred C ₁～C ₅Alkylbenzene is at 120～300 ℃, and preferred 130～250 ℃, more preferred 135～200 ℃ of position rearrangement reactions that substituted alkyl on benzene ring takes place down react.Reaction pressure can be the pressure that under normal pressure or a certain temperature of reaction reactant is in a liquid state, and generally is normal pressure～4.0MPa, preferred normal pressure～3.0MPa.In batch reactor, the weight ratio of charging and catalyzer can be any ratio, preferred 3: 1～50: 1.In flow reactor, the feeding liquid hourly space velocity generally is 0.1～30h ^-1, preferred 0.5～20h ^-1

Said reaction raw materials can be the remaining ingredient of degree of depth alkylate after monoalkylated benzenes is told in distillation of monoalkylated benzenes and monoolefine, or the mixture of this remaining ingredient and trialkyl benzene; Also can be the trialkyl benzene of pure a certain structure, or two or more trialkyl benzene of arbitrary proportion blended.These raw materials can directly use, but industrially generally mix use with a certain amount of dialkyl benzene, to reduce the generation of disproportionation reaction.The content of dialkyl benzene in charging can be 0～80%, preferred 30%～70%.The preferred diethylbenzene of said dialkyl benzene, diisopropylbenzene(DIPB) etc.The preferred triethyl-benzene of said trialkyl benzene, tri-isopropyl benzene, methyl diisopropylbenzene(DIPB) etc.

Two kinds of methods provided by the invention can be carried out in the reactor of multiple pattern, as fixed bed, bubbling bed, slurry bed, intermittence or successive reaction still and catalytic distillation etc.

Between the present invention preparation the position and all the employed catalyzer of position alkylbenzene be the load or the heteropllyacids compound of load not, comprise heteropolyacid, heteropolyacid salt and heteropolyacid acid salt, preferred heteropolyacid and heteropolyacid acid salt, they have following general formula jointly:

M _mH _A-bmXY ₁₂O ₄₀NH ₂O wherein, M is selected from basic metal in the periodic table of elements, second main group, the 3rd main group element metal ion and subgroup element metal ion and ammonium ion, preferred as alkali and ammonium except that Mo, W, V, Nb and Ta etc.X is selected from atoms such as P, Si, Ge or As, preferred P or Si atom.Y is selected from atoms such as Mo, W, V, preferred W atom.N is the number of crystal water, can be 0～30 arbitrary integer.M represents the atomicity of M, can be 0 or other positive number, and a represents [XY ₁₂O ₄₀] ^-aValency, b is the valency of M.When m=0, above-mentioned general formula is expressed as heteropolyacid; When a-bm equaled 0, above-mentioned general formula was expressed as heteropolyacid salt; When m and a-bm all were not equal to zero, above-mentioned general formula was expressed as heteropolyacid acid salt.

The catalyst activity component that the inventive method is used can directly be used in the reaction, but preferably is stated from the porous carrier.The charge capacity of active ingredient (with respect to catalyst weight) can be 1%～60%, and is preferred 5%～50%, more preferably 10～40%.Described porous support is the inorganic or organism of high-ratio surface, as the sieve and silica-sesquioxide and the silico-aluminate of aluminum oxide, silica gel, subgroup metallic element oxide compound, gac, various natural or synthetic.The sieve and silica-sesquioxide and the silico-aluminate of preferred gac, silica gel, aluminum oxide, titanium oxide and various natural or synthetic.The specific surface of porous support can be 20～1200m ²/ g, preferred 80～700 more preferably 120～600m ²Between/the g, the aperture can be 2～50nm, and is preferred 5～30, more preferably 5～15nm.

The heteropllyacids compound that the inventive method adopts is the catalytic material of a class excellent property, and they have higher strength of acid and sour density than zeolites catalyzer, thereby show higher low-temperature catalytic activity, and Stability Analysis of Structures, do not have corrodibility.Compared with prior art, method provided by the invention has the following advantages: (1) has replaced AlCl ₃Catalyzer has been eliminated corrosion and the pollution in the production process, has simplified technical process; (2) temperature of reaction is relatively low, helps suppressing side reaction; (3) low temperature active height, the good stability of catalyzer, activation method is easy.

Following example will give further instruction to the present invention, but the present invention will not be construed as limiting.

Example 1～5 is the heteropllyacids Preparation of catalysts.

Example 1

This case description H ₃PW ₁₂O ₄₀NH ₂The O Preparation of catalysts.

With mol ratio 1: 8 NaH ₂PO ₁₂12H ₂O and Na ₂WO ₄2H ₂O is dissolved in the water of 6 times of weight, is heated to 70 ℃, under the condition of continuously stirring, adds inorganic acid, the pH value of solution is maintained about 0, continue reflux 2h, be cooled to room temperature then, the extraction that adds diethyl ether, extract removed ether after, the solid that obtains is H ₂PW ₁₂O ₄₀

Example 2

This case description Cs _2.5H _0.5PW ₁₂O ₄₀The class Preparation of catalysts.(1) accurately takes by weighing 11.3122gH ₃PW ₁₂O ₄₀21H ₂O is water-soluble to be made into 10% the aqueous solution; (2), accurately take by weighing the anhydrous Cs of 1.4149g by stoichiometric requirement ₂CO ₃(analytical pure) water-soluble to be made into 5% the aqueous solution; (3) under continuously stirring, with Cs ₂CO ₃Solution is added drop-wise in the Salkowski's solution continuously lentamente, after dropwising, continues to stir 30 minutes, boils off redundant moisture then, and the solid of porphyrize gained is required catalyzer Cs _2.5H _0.5PW ₁₂O ₄₀

Example 3

This case description H ₃PW ₁₂O ₄₀/ silica type Preparation of catalysts.1. be 324m with specific surface area ²The silica gel of/g, aperture 9.2nm was handled 4 hours in 150 ℃.Behind the cool to room temperature, it is standby to take by weighing 40.0g.2. accurately take by weighing 11.3122gH ₃PW ₁₂O ₄₀21H ₂O is water-soluble to be made into 15% solution, pours above-mentioned off-the-shelf silica gel rapidly into.Placed 3 hours, drying is removed redundant moisture then, promptly gets 20%H ₃PW ₁₂O ₄₀/ silica gel.

Example 4

This case description Cs _2.5H _0.5PW ₁₂O ₄₀/ gac class Preparation of catalysts 1. is 587m with specific surface area ²The gac of/g, aperture 5.8nm was handled 4 hours in 150 ℃, and behind the cool to room temperature, it is standby to take by weighing 40.0g; 2. by stoichiometric requirement, accurately take by weighing the anhydrous Cs of 1.4149g ₂CO ₃(analytical pure) water-soluble to be made into 2% the aqueous solution; 3. the 40.0g gac is poured into the Cs of step (2) preparation ₂CO ₃In the aqueous solution, left standstill 1 hour, drying removes free-water, then, is warmed up to 150 ℃ and handles 4 hours down, and cooling obtains activated carbon supported Cs ₂CO ₃, i.e. Cs ₂CO ₃/ silica gel.4. accurately take by weighing 11.3122gH ₃PW ₁₂O ₄₀21H ₂O is soluble in water to be made into 15% solution, pours the Cs of above-mentioned preparation rapidly into ₂CO ₃/ silica gel left standstill 3 hours, and drying is removed redundant moisture, got the Cs of charge capacity about 20% _2.5H _0.5PW ₁₂O ₄₀/ gac.

Example 5

This case description Al ₄(SiW ₁₂O ₄₀) ₃/ γ-Al ₂O ₃Class Preparation of catalysts 1. is 195m with specific surface area ²γ-Al of/g, aperture 9.0nm ₂O ₃Handled 4 hours down at 200 ℃, it is standby to take by weighing 40.0g after the cooling; 2. accurately take by weighing 10.9382gH ₄SiW ₁₂O ₄₀15H ₂O is water-soluble to be made into 12% the aqueous solution; 3. by stoichiometric requirement, accurately take by weighing freshly prepd Al (OH) ₃0.3614g, joining in the silicotungstic acid solution of step 2 preparation in batches, violent stirring obtains Al until dissolving fully continuously ₄(SiW ₁₂O ₄₀) ₃The aqueous solution; 4. rapidly with the ready γ-Al of step 1 ₂O ₃Pour Al into ₄(SiW ₁₂O ₄₀) ₃In the aqueous solution, left standstill 3 hours, drying removes redundant moisture then, promptly gets the Al of charge capacity about 20% ₄(SiW ₁₂O ₄₀) ₃/ γ-Al ₂O ₃, note by abridging and be 20%Al _4/3SiW ₁₂/ γ-Al ₂O ₃

Example 6

This example adopts phosphorus heteropoly tungstic acid to make catalyzer, makes the cymene of the ortho para generation m-Methylisopropylbenzene that reacts.

Be reflected in the autoclave of 300ml induction stirring and carry out.Joining material in the reactor and be 100g is made up of toluene (analytical pure) and three kinds of mixture of isomers of cymene and methyl diisopropylbenzene(DIPB), form in detail and be: toluene 40%, p-Methylisopropylbenzene 35.3%, adjacent cymene 13.7%, m-Methylisopropylbenzene 2.1%, methyl diisopropylbenzene(DIPB) 7.2%, other impurity 1.7%.Catalyzer is the phosphorus heteropoly tungstic acid of example 1 preparation, consumption 5g.Reaction conditions is: 140 ℃, and 1.0MPa, reaction times 2h, mixing speed 500 commentaries on classics/min.Reaction is cooled fast to room temperature after finishing.Sampling is formed with the HP5890 gas chromatographic analysis.Analytical results sees Table 1.

Comparative Examples 1

This Comparative Examples adopts AlCl ₃Make catalyzer, make the cymene of the ortho para generation m-Methylisopropylbenzene that reacts.

Reaction unit and reaction raw materials are formed with example 6, and different is that catalyzer is AlCl ₃, consumption 5g.Reaction conditions is: 90 ℃, and 1.0MPa, reaction times 2h, mixing speed 500 commentaries on classics/min.React after 2 hours, add the water termination reaction.Settlement separate organic phase and catalyzer water, organic phase is formed with the HP5890 gas chromatographic analysis.Analytical results sees Table 1.

Comparative Examples 2

This Comparative Examples adopts molecular sieve (H β) to make catalyzer, makes the cymene of the ortho para generation m-Methylisopropylbenzene that reacts.

Reaction unit and reaction raw materials are formed with example 6, and different is that catalyzer is the H beta-molecular sieve, consumption 5g; Reaction conditions is: 200 ℃, and 1.0MPa, reaction times 2h, mixing speed 500 commentaries on classics/min.Reaction is cooled fast to room temperature after finishing.Sampling is formed with the HP5890 gas chromatographic analysis.Analytical results sees Table 1.

Result in the comparison sheet 1 adopts phosphorus heteropoly tungstic acid to make catalyzer as can be known, and temperature of reaction is moderate, and the impurity growing amount compares AlCl ₃Method is lower slightly, though the content of adjacent cymene is higher than AlCl ₃Method, but this result does not influence the following process of product.

Table 1

Project	Comparative Examples 1 Comparative Examples 26
		Catalyzer	????AlCl 3Molecular sieve (H β) phosphorus heteropoly tungstic acid
Temperature of reaction, ℃	????90?????????200????????????140
		Transformation efficiency, the adjacent cymene p-Methylisopropylbenzene of mol%	????86.9???????78.8???????????86.2 ????39.4???????38.5???????????39.4
Relative content between the isomer, the adjacent cymene of mol% m-Methylisopropylbenzene p-Methylisopropylbenzene	????53.9???????50.5???????????53.4 ????42.6???????43.6???????????42.8 ????3.5????????5.9????????????3.8
		Foreign matter content, heavy % is lighter than other component of toluene component	????0.1????????0.4????????????0 ????2.1????????2.4????????????2.0

Example 7～example 10

The different heteropllyacids catalyzer of this group case expedition are converted into the katalysis of m-Methylisopropylbenzene to the cymene of ortho para.

Reaction unit and reaction raw materials are formed with example 6, and different is catalyzer, sees table 2 for details, and catalyst levels all is 5g.Reaction conditions: 140 ℃, 1.0MPa, reaction times 2h, mixing speed 500 commentaries on classics/min.Reaction is cooled fast to room temperature after finishing, and sampling is formed with the HP5890 gas chromatographic analysis.Analytical results sees Table 2.Table 2

Example	????7?????????8??????9??????10
		The catalyzer source	Example 2 examples 3 examples 4 examples 5
Transformation efficiency, the adjacent cymene p-Methylisopropylbenzene of mol%	????85.7?????86.1???86.7????84.7 ????38.8?????39.5???40.5????36.1
		Relative content between the isomer, the adjacent cymene of mol% m-Methylisopropylbenzene p-Methylisopropylbenzene	????53.1?????53.5????53.7???51.3 ????43.0?????42.7????42.6???44.5 ????3.9??????3.8?????3.7????4.2
Foreign matter content, heavy % is lighter than other component of toluene component	????0????????0???????0.1????0 ????1.9??????2.0?????2.0????1.8

Example 11

This example adopts the heteropllyacids compound as catalyst, diisopropyl benzene between the diisopropyl benzene of ortho para being reacted generate.

Be reflected in the autoclave of 300ml induction stirring and carry out.The material that joins in the reactor is the alkylate of 100g isopropyl benzene (analytical pure) and propylene, wherein the part isopropyl benzene is steamed, form in detail and be: isopropyl benzene 35%, p-Diisopropylbenzene 23.6%, adjacent diisopropylbenzene(DIPB) 21.4%, m-Diisopropylbenzene 10.1%, triisopropylbenzene 8.0%, other impurity 0.7%.Catalyst system therefor is the Cs by example 2 preparations _2.5H _0.5PW ₁₂O ₄₀, consumption 5g.Reaction conditions is: 150 ℃, and 1.0MPa, reaction times 2h, mixing speed 500 commentaries on classics/min.Reaction result is as follows:

Transformation efficiency: p-Diisopropylbenzene 13.1mol%, adjacent diisopropylbenzene(DIPB) 78.6mol%

Relative content between the diisopropyl benzene isomer: a position 54.5mol%; Contraposition 37.2mol%; Ortho position 8.3mol%

Example 12

This example adopts the heteropllyacids compound as catalyst, makes the ortho para diethylbenzene be converted into NSC 62102.

Be reflected in the autoclave of 300ml induction stirring and carry out.Join material in the reactor and be ethylbenzene and diethylbenzene that the degree of depth alkylate of 100g benzene (analytical pure) and ethene fractionates out, form in detail and be: ethylbenzene 46.0%, p-Diethylbenzene 21.4%, NSC 62102 10.5%, adjacent diethylbenzene 17.8% mixes triethyl-benzene 3.2%, other impurity 1.1%.Catalyst system therefor is by the Cs of example 4 preparations _2.5H _0.5PW ₁₂O ₄₀/ gac, consumption 5g.Reaction conditions is: 150 ℃, and 1.0MPa, reaction times 2h, mixing speed 500 commentaries on classics/min.Reaction result is as follows:

Transformation efficiency: adjacent diethylbenzene 61.2mol%, p-Diethylbenzene 25.9mol%.

Relative content between three isomer of diethylbenzene: adjacent diethylbenzene 13.9mol%, NSC 62102 54.2mol%, p-Diethylbenzene 31.9mol%.

Example 13

This example adopts the heteropllyacids compound as catalyst, the triisopropylbenzene mixture of isomers is reacted generate equal triisopropylbenzene.

Be reflected in the autoclave of 300ml induction stirring and carry out.The material that joins in the reactor is the degree of depth alkylate of 100g isopropyl benzene (analytical pure) and propylene, and wherein isopropyl benzene and part diisopropyl benzene are steamed, and forms in detail to be: diisopropyl benzene 42%, 1,2,3-triisopropylbenzene 11.7%, 1,2,4-triisopropylbenzene 30.5%, 1,3,5-tri-isopropyl benzene 7.1% mixes tetraisopropylbenzene 6.0%, other impurity 2.7%.Catalyst system therefor is the 25%H by example 3 preparations ₃PW ₁₂O ₄₀/ silica gel, consumption 5g.Reaction conditions is: 150 ℃, and 1.0MPa, reaction times 2h, mixing speed 500 commentaries on classics/min.Reaction result is as follows:

Transformation efficiency: 1,2,3-triisopropylbenzene 94.9mol%, 1,2,4-triisopropylbenzene 44.6mol%.

Relative content between the diisopropyl benzene isomer: 1,2,3. triisopropylbenzene 1.2mol%; 1,2,4-triisopropylbenzene 34.3mol%; 1,3,5-tri-isopropyl benzene 64.5mol%.

Example 14～example 18

This group case expedition temperature of reaction is converted into the influence of m-Methylisopropylbenzene reaction to the cymene of ortho para.

The pan feeding of reaction is formed with example 6, and used catalyzer is the 25%H by example 3 preparations ₃PW ₁₂O ₄₀/ silica gel, reaction unit adopts micro fixed-bed reactor, and tube inner diameter is Ф 12mm, and loaded catalyst is 10g, and reaction pressure is 1.0MPa, and the liquid hourly space velocity of pan feeding is 2h-1, and temperature of reaction and reaction result see Table 3.Table 3

Example	????14?????15?????16?????17?????18
		Temperature of reaction, ℃	????120????150????180????210????240
Transformation efficiency, the adjacent cymene p-Methylisopropylbenzene of mol%	????36.5???86.4???86.8???84.8???78.7 ????19.0???39.2???42.3???43.7???46.3
		Relative content between the isomer, the adjacent cymene of mol% m-Methylisopropylbenzene p-Methylisopropylbenzene	????26.7???53.6????55.1???56.7??56.5 ????56.2???42.7????41.2???39.2??37.7 ????17.1???3.7?????3.7????4.1???5.8
Foreign matter content, heavy % is lighter than toluene component and overweights toluene component	????0??????0???????0.1????0.2???0.5 ????1.7????1.9?????2.2????2.5???2.9

Example 19～example 21

This group case expedition material is formed the influence that the cymene of ortho para is converted into the m-Methylisopropylbenzene reaction.

React used catalyzer, reaction unit and loaded catalyst with example 14, reaction conditions is 150 ℃, 1.0MPa, 2.0h ^-1Different is the pan feeding composition of reaction, wherein:

The pan feeding of example 19 is toluene (analytical pure) and three kinds of mixture of isomers of cymene, specifically consists of: toluene 40%, p-Methylisopropylbenzene 40.6%, adjacent cymene 15.8%, m-Methylisopropylbenzene 2.5%, impurity 1.2%;

The pan feeding of example 20 is three kinds of mixture of isomers of cymene, specifically consists of: p-Methylisopropylbenzene 67.5%, adjacent cymene 26.2%, m-Methylisopropylbenzene 4.1%, impurity 2.2%;

The pan feeding of example 21 is that mol ratio is 5: 1 toluene and propylene at 90 ℃ alkylation reaction product, specifically consists of: toluene 75.5%, p-Methylisopropylbenzene 7.5%, adjacent cymene 9.1%, m-Methylisopropylbenzene 4.3%, methyl diisopropylbenzene(DIPB) 3.3%, impurity 0.3%.

Reaction result sees Table 4.Table 4

Example	????19??????20??????21
		Transformation efficiency, the adjacent cymene p-Methylisopropylbenzene of mol%	????87.5????87.3????90.1 ????57.2????57.0????1.3
Relative content between the isomer, the adjacent cymene of mol% m-Methylisopropylbenzene p-Methylisopropylbenzene	????61.8????58.9????65.6 ????34.3????35.8????30.7 ????3.9?????4.1?????3.7
		Foreign matter content, the non-aromatic component by-product of heavy % by-product aromatic component	????0???????0.1?????0 ????1.5?????2.8?????0.1

Claims (18)

1. the preparation method of position alkylbenzene between a kind comprises: in load or not under the katalysis of the heteropllyacids compound of load, make the C that contains dialkyl benzene ₁～C ₁₀Alkylbenzene carries out the reaction of alkyl position rearrangement reaction under 120～300 ℃.

2. according to the described preparation method of claim 1, it is characterized in that the alkyl carbon number of alkylbenzene is C ₁～C ₅

3. according to the described preparation method of claim 1, it is characterized in that temperature of reaction is 130～250 ℃.

4. according to the described preparation method of claim 1, it is characterized in that said dialkyl benzene is selected from the neighbour, to first and second benzene of a, position, adjacent, to the cymene of a, position, adjacent, to the diethylbenzene of a, position and neighbour, to the diisopropylbenzene(DIPB) of a, position.

5. according to the described preparation method of claim 1, it is characterized in that, contain 0～80% monoalkylated benzenes and 0～20% trialkyl benzene in the said alkylbenzene.

6. equal preparation method of position alkylbenzene comprises: in load or not under the katalysis of the heteropllyacids compound of load, make the C that contains trialkyl benzene ₁～C ₁₀Alkylbenzene carries out the reaction of alkyl position rearrangement reaction under 120～300 ℃.

7. according to the described preparation method of claim 6, it is characterized in that the alkyl carbon number of alkylbenzene is C ₁～C ₅

8. according to the described preparation method of claim 6, it is characterized in that temperature of reaction is 130～250 ℃.

9. according to the described preparation method of claim 6, it is characterized in that said trialkyl benzene is selected from triethyl-benzene, tri-isopropyl benzene and methyl diisopropylbenzene(DIPB).

10. according to the described preparation method of claim 6, it is characterized in that, contain 0～80% dialkyl benzene in the said alkylbenzene.

11., it is characterized in that said heteropllyacids compound is selected from the compound with following general formula according to claim 1 or 6 described preparation methods:

M _mH _A-bmXY ₁₂O ₄₀NH ₂O wherein, M is selected from basic metal in the periodic table of elements, second main group, the 3rd main group element metal ion and subgroup element metal ion and ammonium ion except that Mo, W, V, Nb and Ta, X is selected from P, Si, Ge and As atom, Y is selected from Mo, W and V atom, n is 0～30 arbitrary integer, m represents the atomicity of M, and a represents [XY ₁₂O ₄₀] ^-aValency, b is the valency of M.

12., it is characterized in that M is selected from basic metal and ammonium according to the described preparation method of claim 11.

13., it is characterized in that X is selected from P and Si atom according to the described preparation method of claim 11.

14., it is characterized in that Y is the W atom according to the described preparation method of claim 11.

15., it is characterized in that a-bm is not equal to 0 according to the described preparation method of claim 11.

16. according to claim 1 or 6 described preparation methods, it is characterized in that said heteropllyacids is compound loaded on porous support, charge capacity is 1%～60%.

17., it is characterized in that said porous support is selected from aluminum oxide, silica gel, subgroup metallic element oxide compound, gac, sieve and silica-sesquioxide and silico-aluminate according to the described preparation method of claim 16.

18., it is characterized in that the specific surface of said porous support is 20～1200m according to the described preparation method of claim 17 ²/ g, the aperture is 2～50nm.