CN103539601B - For toluene and methanol side chain alkylation ethylbenzene and cinnamic method - Google Patents
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- CN103539601B CN103539601B CN201210240056.5A CN201210240056A CN103539601B CN 103539601 B CN103539601 B CN 103539601B CN 201210240056 A CN201210240056 A CN 201210240056A CN 103539601 B CN103539601 B CN 103539601B
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Abstract
The present invention relates generally to a kind of for toluene and methanol side chain alkylation ethylbenzene and cinnamic method, there is toluene conversion low with ethylbenzene with selectivity of styrene low problem when the catalyzer mainly used in solution prior art reacts for methylbenzene methanol side chain alkylation.The present invention is by adopting with toluene and methyl alcohol for raw material, and in raw material, toluene and methanol molar ratio are (0.1 ~ 10): 1, are 200 ~ 600 DEG C in temperature of reaction, and reaction pressure is 0 ~ 0.5MP, and raw material weight air speed is 0.5 ~ 10 hour
-1condition under, raw material and catalyst exposure, reaction generates ethylbenzene and vinylbenzene; Described catalyzer is selected from least one in X molecular sieve or Y molecular sieve, catalyzer solves this problem by the technical scheme that at least two kinds in potassium ion, rubidium ion or cesium ion carry out ion-exchange before use respectively preferably, can be used for the reaction of methylbenzene methanol side chain alkylation and prepares in ethylbenzene and cinnamic industrial production.
Description
Technical field
The present invention relates to a kind of for toluene and methanol side chain alkylation ethylbenzene and cinnamic method.
Background technology
Styrene monomer is a kind of important Organic Chemicals, is mainly used in the production of the products such as polystyrene, (ABS) resin, styrene-butadiene rubber(SBR), unsaturated polyester.In addition, also can be used for pharmacy, dyestuff or produce farm chemical emulgent and dressing agent etc., purposes is very extensive.The output of styrene series resin is only second to PE, PVC and comes in third in synthetic resins.Current most of technical benzene ethene reacts generation ethylbenzene by benzene and ethene through Friedel-Craft, then get through catalytic dehydrogenation.This method flow process compared with long, side reaction is many, energy consumption is high, raw materials cost accounts for 85% of production variable cost, and production cost is higher.Toluene and methanol alkylation produce a cinnamic route having a potential application foreground, and the X-type that Sidorenko in 1967 etc. exchange with alkalimetal ion first and y-type zeolite are that catalyzer successfully uses toluene and methanol-fueled CLC ethylbenzene and vinylbenzene.Compared with traditional technology, this method has the advantages such as raw material sources are wide, cost is low, energy consumption is low, pollution is few.Thus this reacts and is just subject to the people's attention once report, and the research about this respect also starts to increase.
The catalyzer of methylbenzene methanol side chain alkylation preparation of styrene belongs to solid base catalyst, but catalytic process is a soda acid concerted catalysis reaction, and takes as the leading factor with the catalysis of basic active position.The acid potential energy of catalyzer plays the effect of stable toluene phenyl ring, and the methyl group of alkaline potential energy activation Toluene and methyl alcohol.First methyl alcohol is decomposed into formaldehyde in the heart in alkali, and toluene is adsorbed on acid site, and its pendant methyl is activated by alkali center, and then formaldehyde produces vinylbenzene with the methyl reaction activated, and the H-H reaction of part styrene and generation generates ethylbenzene.If catalyzer alkalescence is excessively strong, formaldehyde can be made to decompose further, produce more hydrogen and ethylbenzene simultaneously; If acidity of catalyst is excessively strong, then alkylation and the toluene disproportionation of phenyl ring can occur, generate benzene and dimethylbenzene, so require that catalyzer has suitable soda acid coupling, the existence of phenyl ring simultaneously requires that catalyzer has certain spatial hole structure.
The reaction of methylbenzene methanol side chain alkylation once conducted extensive research on multiple catalysts.Many molecular sieves are as X, Y, L, β, ZSM-5, and some basic oxide are as MgO, MgO-TiO
2, CaO-TiO
2the research that is all in the news is applied in the reaction of catalysis methylbenzene methanol side chain alkylation, as JOURNALOFCATALYSIS173,490-500 (1998) and CN101623649A, CN101623650A.Result of study finds, want to reach good side chain alkylation catalytic effect, catalyzer must meet 4 requirements below: catalyzer must have enough basic center activation methanol conversion to be methylating reagent formaldehyde; Weak Lewis acid site is had to come stable toluene and its methyl of polarization; Toluene and methyl alcohol will have a good stoichiometric adsorption equilibrium on a catalyst; Catalyzer must have micropore canals structure.Therefore, show the result of study of some zeolite catalysis activity, the X-type zeolite of alkali metal cation-exchanged is the catalyzer of relative efficiency.The reactive behavior of y-type zeolite is inferior to X-type zeolite.And other reactive behavior as zeolites such as L, β, ZSM-5 types is all undesirable, and some do not have the basic oxide of microvoid structure, as MgO, MgO-TiO
2and CaO-TiO
2etc. only having very low activity.Document US5015796 discloses and uses the zeolite molecular sieve of alkalimetal ion or alkaline-earth metal ions process to react for methylbenzene methanol side chain alkylation, but all only relate to a kind of ion, sodium ion exchange is not thorough, result toluene conversion is only 6.6%, ethylbenzene and vinylbenzene add up to selectivity only to reach 0.4%, there is toluene conversion low with ethylbenzene with the lower problem of selectivity of styrene.
Summary of the invention
It is low with ethylbenzene with the low problem of selectivity of styrene that technical problem to be solved by this invention is that the catalyzer used in prior art exists toluene conversion when reacting for methylbenzene methanol side chain alkylation, provide a kind of newly for toluene and methanol side chain alkylation ethylbenzene and cinnamic method.It is high that the method has toluene conversion, ethylbenzene and the high feature of selectivity of styrene.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of be used for toluene and methanol side chain alkylation ethylbenzene and cinnamic method, with toluene and methyl alcohol for raw material, in raw material, toluene and methanol molar ratio are (0.1 ~ 10): 1, it is 200 ~ 600 DEG C in temperature of reaction, reaction pressure is 0 ~ 0.5MP, and raw material weight air speed is 0.5 ~ 10 hour
-1condition under, raw material and catalyst exposure, reaction generates ethylbenzene and vinylbenzene; Described catalyzer is selected from least one in X molecular sieve or Y molecular sieve, catalyzer before use respectively with concentration be 0.5 ~ 2.5 mol/L containing potassium ion solution, containing rubidium ion solution or containing cesium ion solution at least two kinds carry out ion-exchange, exchange temperature is 50 ~ 90 DEG C, each swap time is 1 ~ 3 hour, and solid-liquid weight ratio is 1: (5 ~ 10).
In technique scheme, catalyzer preferred version is for being selected from SiO
2/ Al
2o
3be 1 ~ 7 X molecular sieve or Y molecular sieve at least one, more preferably scheme is for being selected from SiO
2/ Al
2o
3it is the X molecular sieve of 2 ~ 3.After ion-exchange, the ion-exchange degree that at least two kinds of alkalimetal ions in catalyzer in potassium ion, rubidium ion or cesium ion exchange sodium ion is 10 ~ 90%.Preferred version of the present invention is that catalyzer carries out ion-exchange with the solution containing potassium ion, the solution containing rubidium ion and the solution containing cesium ion before use successively.The described solution preferred version containing potassium ion is be selected from least one in potassium hydroxide solution or potassium nitrate solution, the described solution preferred version containing rubidium ion is be selected from least one in rubidium hydroxide or rubidium nitrate, and the described solution preferred version containing cesium ion is be selected from least one in cesium hydroxide or cesium nitrate.In raw material, toluene and methanol molar ratio preferable range are (2 ~ 7): 1, and temperature of reaction preferable range is 350 ~ 500 DEG C, and reaction pressure preferable range is 0 ~ 0.2MPa, and raw material weight air speed preferable range is 1 ~ 8 hour
-1.
The inventive method can be carried out in continuous flow reactor of fixed bed, and its process is summarized as follows: the flat-temperature zone of reactor put into by the catalyzer getting aequum, and catalyzer bottom quartz sand is filled.At the temperature, pressure of setting, by toluene and methanol mixed, enter reactor upper end after delivering to preheater and nitrogen mixture with micro pump, flow through beds and carry out catalyzed reaction, reaction product directly enters gas-chromatography analysis with valve injection.
The activity and selectivity of catalyzer calculates according to following formula:
The order (potassium, rubidium, cesium ion) that the inventive method increases according to ionic radius, carries out ion-exchange with the solution continuous process containing potassium, rubidium, caesium to the X of Different Silicon aluminum ratio or Y molecular sieve, substantially increases ion-exchange degree, substantially increase catalytic effect.Adopt the inventive method, be 3: 1 at toluene and methanol molar ratio, temperature of reaction is 415 DEG C, and reaction pressure is 0MPa, and raw material weight air speed is 2.5 hours
-1condition under, use ratio of methanol can up to 57.29%, and ethylbenzene vinylbenzene overall selectivity can reach 96.65%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Get silica alumina ratio SiO
2/ Al
2o
310 grams, the NaX molecular sieve of=2.19, at 80 DEG C, carries out ion-exchange 2 hours in the KOH solution of 100 milliliter of 1 mol/L, exchanges 3 times.Then in the CsOH solution of 50 milliliter of 1 mol/L, carry out ion-exchange, exchange 3 times, filter rear 100 DEG C of dryings 10 hours.After exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 87.8%
By catalyst tablet forming 40 ~ 60 object beaded catalyst obtained above, load reactor, normal pressure, methylbenzene methanol mol ratio be 3:1, at 2.5 hours
-1liquid air speed, 415 DEG C, N
2flow velocity is carry out activity rating under the condition of 10 ml/min, and the results are shown in Table 1.
[embodiment 2]
Get silica alumina ratio SiO
2/ Al
2o
3the NaX molecular sieve of=2.57 is according to the method Kaolinite Preparation of Catalyst of [embodiment 1], and after exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 86.2%
Carry out activity rating according to the method for [embodiment 1], the results are shown in Table 1.
[embodiment 3]
Get silica alumina ratio SiO
2/ Al
2o
3the NaY molecular sieve of=5.58 is according to the method Kaolinite Preparation of Catalyst of [embodiment 1], and after exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 82.8%
Carry out activity rating according to the method for [embodiment 1], the results are shown in Table 1.
[embodiment 4]
Get silica alumina ratio SiO
2/ Al
2o
310 grams, the NaX molecular sieve of=2.19, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L
3carry out ion-exchange 2 hours in solution, exchange 3 times; Then at the CsNO of 50 milliliter of 1 mol/L
3carry out ion-exchange in solution, exchange 3 times; Filter rear 100 DEG C of dryings 10 hours.After exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 83.6%
Carry out activity rating according to the method for [embodiment 1] to catalyzer, the results are shown in Table 1.
[embodiment 5]
Get silica alumina ratio SiO
2/ Al
2o
310 grams, the NaX molecular sieve of=2.19, at 80 DEG C, at the KNO of 100 milliliter of 1 mol/L
3carry out ion-exchange 2 hours in solution, exchange 3 times; Then in the CsOH solution of 50 milliliter of 1 mol/L, carry out ion-exchange, exchange 3 times; Filter rear 100 DEG C of dryings 10 hours.After exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 84.3%
Carry out activity rating according to the method for [embodiment 1] to catalyzer, the results are shown in Table 1.
[embodiment 6]
Get silica alumina ratio SiO
2/ Al
2o
310 grams, the NaX molecular sieve of=2.19, at 80 DEG C, carries out ion-exchange 2 hours in the KOH solution of 100 milliliter of 1 mol/L, exchanges 2 times; Then in the RbOH solution of 50 milliliter of 1 mol/L, carry out ion-exchange, exchange 2 times; Finally in the CsOH solution of 50 milliliter of 1 mol/L, carry out ion-exchange, exchange 2 times; Filter rear 100 DEG C of dryings 10 hours.After exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 85.7%
Carry out activity rating according to the method for [embodiment 1] to catalyzer, the results are shown in Table 1.
[comparative example 1]
Get silica alumina ratio SiO
2/ Al
2o
310 grams, the NaX molecular sieve of=2.19, at 80 DEG C, carries out ion-exchange 2 hours in the KOH solution of 100 milliliter of 1 mol/L, exchanges 3 times, filters rear 100 DEG C of dryings 10 hours.After exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 86.0%
Carry out activity rating according to the method for [embodiment 1] to catalyzer, the results are shown in Table 1.
[comparative example 2]
Get silica alumina ratio SiO
2/ Al
2o
310 grams, the molecular sieve of=2.19NaX, at 80 DEG C, carries out ion-exchange 2 hours in the CsOH solution of 100 milliliter of 1 mol/L, exchanges 3 times, filters rear 100 DEG C of dryings 10 hours.After exchange, in catalyzer, alkalimetal ion exchanges the ion-exchange degree of sodium ion in molecular sieve is 64.2%
Carry out activity rating according to the method for [embodiment 1] to catalyzer, the results are shown in Table 1.
Table 1
[embodiment 7 ~ 14]
Change examination condition, investigate the catalytic performance of catalyzer under difference examination condition of [embodiment 2] and [embodiment 6].Its examination condition and appraisal result list in table 2.
Table 2
Claims (5)
1. one kind for toluene and methanol side chain alkylation ethylbenzene and cinnamic method, with toluene and methyl alcohol for raw material, in raw material, toluene and methanol molar ratio are (0.1 ~ 10): 1, it is 200 ~ 600 DEG C in temperature of reaction, reaction pressure is 0 ~ 0.5MPa, and raw material weight air speed is 0.5 ~ 10 hour
-1condition under, raw material and catalyst exposure, reaction generates ethylbenzene and vinylbenzene; Described catalyzer is selected from SiO
2/ Al
2o
3be 1 ~ 7 X molecular sieve or Y molecular sieve at least one, catalyzer before use respectively with concentration be 0.5 ~ 2.5 mol/L containing potassium ion solution, containing rubidium ion solution or containing cesium ion solution at least two kinds carry out ion-exchange, exchange temperature is 50 ~ 90 DEG C, 1 ~ 3 hour each swap time, solid-liquid weight ratio is 1: (5 ~ 10); After ion-exchange, the ion-exchange degree that at least two kinds of alkalimetal ions in molecular sieve catalyst in potassium ion, rubidium ion or cesium ion exchange sodium ion is 10 ~ 90%.
2., according to claim 1 for toluene and methanol side chain alkylation ethylbenzene and cinnamic method, it is characterized in that catalyzer is selected from SiO
2/ Al
2o
3it is the X molecular sieve of 2 ~ 3.
3., according to claim 1 for toluene and methanol side chain alkylation ethylbenzene and cinnamic method, it is characterized in that catalyzer carries out ion-exchange with the solution containing potassium ion, the solution containing rubidium ion and the solution containing cesium ion before use successively.
4. according to claim 1 for toluene and methanol side chain alkylation ethylbenzene and cinnamic method, it is characterized in that the described solution containing potassium ion is selected from least one in potassium hydroxide solution or potassium nitrate solution, the described solution containing rubidium ion is selected from least one in rubidium hydroxide or rubidium nitrate, and the described solution containing cesium ion is selected from least one in cesium hydroxide or cesium nitrate.
5. according to claim 1 for toluene and methanol side chain alkylation ethylbenzene and cinnamic method, it is characterized in that in raw material, toluene and methanol molar ratio are (2 ~ 7): 1, temperature of reaction is 350 ~ 500 DEG C, reaction pressure is 0 ~ 0.5MPa, and raw material weight air speed is 1 ~ 8 hour
-1.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210240056.5A CN103539601B (en) | 2012-07-12 | 2012-07-12 | For toluene and methanol side chain alkylation ethylbenzene and cinnamic method |
| BR112014031324-5A BR112014031324B1 (en) | 2012-07-12 | 2013-07-04 | alkylation process for alkyl benzenes |
| CA2871301A CA2871301C (en) | 2012-07-12 | 2013-07-04 | An alkylating process for alkyl benzenes |
| PCT/CN2013/000817 WO2014023079A1 (en) | 2012-07-12 | 2013-07-04 | Alkylbenzene alkylation method |
| US14/397,706 US9802876B2 (en) | 2012-07-12 | 2013-07-04 | Alkylating process for alkyl benzenes |
| RU2014143113A RU2627695C2 (en) | 2012-07-12 | 2013-07-04 | Method of alkylation of alkyl benzenes |
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| CN201210240056.5A CN103539601B (en) | 2012-07-12 | 2012-07-12 | For toluene and methanol side chain alkylation ethylbenzene and cinnamic method |
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| CN103539601B true CN103539601B (en) | 2015-11-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926580B (en) * | 2014-03-17 | 2017-04-19 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene and styrene through toluene and methanol side chain alkylation |
| CN106278800A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | Toluene and the method for methanol side chain alkylation |
| CN106607073B (en) * | 2015-10-22 | 2019-10-11 | 中国石油化工股份有限公司 | Methylbenzene methanol side chain alkylation prepares ethylbenzene phenylethylene catalyst and application thereof |
| CN106179459B (en) * | 2016-07-15 | 2019-04-02 | 中国科学院大连化学物理研究所 | A kind of preparation and its application of high-performance Benzyl Side-Chain alkylation catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4463204A (en) * | 1983-04-22 | 1984-07-31 | Exxon Research & Engineering Co. | Process for alkylating toluene with methanol to form styrene using a low sodium content potassium/cesium modified zeolite catalyst composition |
| CN101623650A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst through toluene-methanol side chain alkylation |
| CN101623649A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Alkaline molecular sieve catalyst for preparing styrene |
-
2012
- 2012-07-12 CN CN201210240056.5A patent/CN103539601B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4463204A (en) * | 1983-04-22 | 1984-07-31 | Exxon Research & Engineering Co. | Process for alkylating toluene with methanol to form styrene using a low sodium content potassium/cesium modified zeolite catalyst composition |
| CN101623650A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst through toluene-methanol side chain alkylation |
| CN101623649A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Alkaline molecular sieve catalyst for preparing styrene |
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