CN102964203A - High-selectivity method for synthesizing styrene through methanol and toluene side chain alkylation - Google Patents
High-selectivity method for synthesizing styrene through methanol and toluene side chain alkylation Download PDFInfo
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- CN102964203A CN102964203A CN2012104659979A CN201210465997A CN102964203A CN 102964203 A CN102964203 A CN 102964203A CN 2012104659979 A CN2012104659979 A CN 2012104659979A CN 201210465997 A CN201210465997 A CN 201210465997A CN 102964203 A CN102964203 A CN 102964203A
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Abstract
The invention relates to a high-selectivity method for synthesizing styrene through methanol and toluene side chain alkylation, namely a high-selectivity method for preparing styrene through toluene and methanol alkylation by use of an alkaline molecular sieve based catalyst under the condition of taking carbon dioxide as a reaction medium. In the method for synthesizing styrene through toluene and methanol alkylation by use of a molecular sieve based catalyst containing metal aid modification, in the presence of a carbon dioxide medium, the mixture of toluene and methanol at a molar ratio of 2.0-8.0 is used as a raw material, the reaction temperature is 350-540 DEG C, the toluene reaction airspeed is kept at 0.1-4.0/h, the pressure of the reaction medium is kept at 0.1-6.0MPa, and the molar ratio of carbon dioxide to hydrocarbon is kept at 0.5-10.0. According to the invention, by taking a large amount of excessive greenhouse gas carbon dioxide as a reaction medium, the styrene is prepared with a high yield, and the problems of many side reactions and poor selectivity in the existing styrene synthesis technology through toluene and methanol alkylation are solved; and moreover, the reaction stability can be improved so that the catalyst stability and styrene selectivity in the styrene synthesis through toluene and methanol alkylation meet the requirements of industrial application.
Description
Technical field
The present invention relates to a kind of method of highly selective methanol toluene side chain alkylation synthesizing styrene, namely adopt under the reaction medium of carbonic acid gas, realize the novel method of toluene and the reaction of methanol alkylation high selectivity vinylbenzene continous-stable by molecular sieve catalyst.
Background technology
Vinylbenzene is as the main raw material of synthetic polystyrene, styrene-butadiene rubber(SBR), ion exchange resin, and it is the fourth-largest ethylene derivative product that is only second to PE, PVC, EO.Cinnamic demand is always in continuous growth, and the vinylbenzene production capacity situation of China is that supply falls short of demand always, about more than 300 ten thousand tons of annual import volume.And present its main industrial mode of production-ethylbenzene dehydrogenation method synthesizing styrene, exist side reaction many, produce a large amount of greenhouse gases and the high problem of energy consumption.Adopt alkaline molecular sieve as catalyzer, can effectively reduce energy consumption by methylbenzene methanol side chain alkylation reaction synthesizing styrene, Decrease production cost, and can reduce the discharging of greenhouse gases.But, in the reaction of methylbenzene methanol side chain alkylation synthesizing styrene, because the hydrogen generation addition reaction that vinylbenzene and methyl alcohol are taken off generates ethylbenzene, reduce the selectivity of styrene in the reaction product.Simultaneously, because catalyzer knot carbon in the reaction of methylbenzene methanol side chain alkylation is serious, cause the rapid deactivation of catalyzer.So the selectivity and the reaction stability that how to improve synthesizing styrene are the difficult points of methylbenzene methanol side chain alkylation reaction technology research always.
Methylbenzene methanol side chain alkylation synthesizing styrene reaction be the earliest the sixties in last century by Sidorenko Yu N etc. (
Yu.N.Sidorenko, P.N.Galich, V.S.Gutyrya. " Method for the simultaneous preparation of ethylbenzene and styrene; " USSR Inventor ' s Certificate 1888958, IPC C07c, Bull. No. 23, Publ. November 17,1966.) propose, they think that the alkylation of toluene methanol synthesizing styrene is is soda acid concerted catalysis reaction on the main molecular sieve catalyst by alkalescence.For this methylbenzene methanol side chain alkylation reaction mechanism, basically identical viewpoint is: the generation that at first is formaldehyde, formaldehyde is adsorbed by the acid site, toluene and acid sites interact simultaneously, its pendant methyl is activated by the alkali center, generates the vinylbenzene of ADSORPTION STATE by the reaction of carbanion mechanism generation side chain alkylation with formaldehyde again.
CH
3OH→HCHO+H
2
In above-mentioned this reaction process, because can carrying out with the hydrogen that methyl alcohol is taken off addition reaction, the vinylbenzene that generates generates ethylbenzene, so that selectivity of styrene and productive rate reduce greatly.
Although toluene and methyl alcohol are considered to the mode of production of alternative traditional technology by molecular sieve catalytic alkylation synthesizing styrene always, the low problem of tying fast the carbon inactivation with catalyzer of reaction preference has limited its process of industrialization.People launch research for these two key technical problems for this reason, and emphasis focuses in the development of various new catalysts.US Patent No. 4483936 has reported that the X-type molecular sieve activity of basic metal Cs, Rb modification is higher, wherein use the X-type molecular sieve activity of CsOH direct impregnation modification best, the single-component modified X-type molecular sieve property selected of Cs reaches 35%, total recovery has reached 15%, this class basic metal has significantly strengthened the molecular sieve surface alkalinty, improved catalytic performance, but the problem of poor catalyst stability is unresolved.Patent US 5015796 has reported that a kind of X molecular sieve of the B of employing modification is catalyzer, has improved the reaction stability of methylbenzene methanol synthesizing styrene; And X molecular sieve is after load B, and its temperature of reaction reduces greatly, but not obvious on cinnamic selectivity impact, selectivity of styrene is still lower.Chinese patent CN 200810043611 is by being exchanged into H type molecular sieve with molecular sieve with ammonium salt first, exchange with an alkali metal salt again after the roasting, become alkaline molecular sieve after drying, the roasting, to be selected from again B, P and be selected from least a element dipping method in basic metal, the alkaline-earth metal, catalyzer is made in load, solved preferably that the molecular sieve catalyst structure is destroyed easily and the problem that causes poor stability, but the selectivity of methylbenzene methanol side chain alkylation catalyst for preparing phenylethylene is lower.
In sum, only adopt at present technology that the preparation method of catalyzer innovates change by way of, can not solve simultaneously the problem that selectivity of styrene is low, reaction stability is poor that exists in the existing methylbenzene methanol side chain alkylation preparation of styrene technology, limited the practical application of methylbenzene methanol side chain alkylation reaction synthesizing styrene technology, so even to this day, this synthesizing styrene processing technology routine fails to realize industrialization always.
Reference:
1.?Sidorenko?YuN?,?Galich?P?N?,?Gutyrya?V?S.?Method?for?the?simultaneous?preparation?of?ethylbenzene?and?styrene?USSR,?1888958[P].?1966-11-17
2.?Mark?L.Unland?;?George?E.Barker?.?US?Patent?No.?5015796.(1978)
3. open spring force, Shao Ying etc. CO
2Selective oxidation preparing styrene from ethylbenzene Research advance in catalysts for production [J] Chemical Manufacture and technology .2009,16(4).
Summary of the invention
The object of the present invention is to provide a kind of method of highly selective methanol toluene side chain alkylation synthesizing styrene.
The invention provides a kind ofly under the reaction medium of carbonic acid gas, realize that by alkaline molecular sieve catalyst the cinnamic continous-stable of toluene and methanol alkylation high selectivity reacts new solution.It adopts carbonic acid gas as reaction medium, with the molecular sieve that contains the metal promoter modification as catalyzer, prepare the cinnamic while in high yield, not only solve toluene and methanol alkylation and prepared the low problem of selectivity of styrene, also effectively restrain on the catalyzer knot carbon and caused the process of inactivation, thereby also solved toluene and methanol alkylation prepares the poor problem of vinylbenzene reaction stability.And the technology of the present invention also environmental protection ground utilization has transformed excessive greenhouse gases carbonic acid gas.
The method of the highly selective methanol toluene side chain alkylation synthesizing styrene that the present invention proposes, concrete steps are as follows:
On fixed-bed reactor, realize that by the alkaline molecular sieve catalyst that contains metal promoter toluene and methanol side chain alkylation come the method for synthesizing styrene; The mixture that forms take toluene and methyl alcohol is as raw material, and toluene and methyl alcohol mol ratio are 2.0:1 ~ 8.0:1, and maintenance toluene reaction velocity is 0.1 ~ 4 h
-1, under 350 ~ 540 ℃ temperature of reaction, reaction medium adopts carbonic acid gas, and control reaction medium pressure is 0.1～6.0MPa, and the mol ratio of carbonic acid gas and hydrocarbon is 0.5:1～10.0:1.
Among the present invention, reaction medium pressure is 0.1～2.0MPa, and the mol ratio of carbonic acid gas and hydrocarbon is 1.0:1～6.0:1.
Among the present invention, temperature of reaction is 400～500 ℃, and the toluene reaction velocity is 0.5～3.0h
-1
Among the present invention, the mol ratio of toluene and methyl alcohol is 4.0:1～8.0:1.
Among the present invention, molecular sieve catalyst adopt zeolite molecular sieve, zeolite molecular sieve be in ZSM-5, MCM-22, X-type molecular sieve or the Y zeolite any.
Among the present invention, it is 0.5 wt%～8 wt% of zeolite weight that described metal promoter adopts at least a among Ca, K, Zn, Cs, Sr, Bi or the Ba, metal promoter add-on.
Use toluene of the present invention and methanol alkylation to prepare the vinylbenzene method, it is high to produce the vinylbenzene productive rate, and reaction stability is good, 500 hours obvious catalyst deactivation signs of nothing of successive reaction in fixed bed catalytic reactor.
The transformation efficiency of toluene and cinnamic optionally method of calculation are as follows among the present invention:
The technical characterstic of the inventive method is as a weak oxidant with carbonic acid gas, utilize the redox generation carbon monoxide CO of carbonic acid gas and hydrogen and the reaction of water, prevent that hydrogen and the vinylbenzene addition of taking off from generating ethylbenzene, thereby improved the selectivity of styrene product.On the other hand, also utilized in the methods of the invention the reaction of the redox generation carbon monoxide CO of knot carbon composition on carbonic acid gas and the catalyzer, effectively restrained and tied the process that carbon causes inactivation on the catalyzer, thereby toluene and methanol alkylation synthesizing styrene reaction stability have been improved, so the inventive method is by the technological approaches of reaction process coupling, solved dexterously the difficult problem of stable in existing toluene and the methanol alkylation synthesizing styrene technique and poor selectivity, make the catalyst stability of toluene and methanol alkylation synthesizing styrene and the requirement that selectivity of styrene has satisfied industrial application preferably, have good technology using value.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1: an amount of granulated glass sphere of packing in the reaction tubes bed bottom of the miniature fixed bed catalytic reactor of internal diameter 1.5cm first, on granulated glass sphere, spread the skim silica wool, the reaction tubes of again the ZSM-5 molecular sieve catalyzer of the cylindric Ca modification of 3.0 ~ 5.0g being packed into, the upper strata an amount of granulated glass sphere that recharges, through temperature programming to 420 in 100 minutes ℃, pass into carbonic acid gas, and pass into the reaction raw materials that consists of toluene and methanol=5(mol/mol) with volume pump, keeping the toluene mass space velocity is WHSV=1.0h
-1, maintenance carbonic acid gas/hydrocarbon=2(mol/mol), keeping reaction medium pressure is 0.3MPa, the reaction stream fluid is got the upper strata organism as the product sample, through gas chromatographic analysis, calculates toluene conversion and the cinnamic selectivity of reaction.
Embodiment 2: this implementation column difference from Example 1 is to use the ZSM-5 molecular sieve of Zn modification to be 1(mol/mol as catalyzer, maintenance carbonic acid gas/hydrocarbon), other reaction conditionss are identical with embodiment 1.
Embodiment 3: the present embodiment difference from Example 1 is to use the ZSM-5 molecular sieve of Cs modification to be 2.5(mol/mol as catalyzer, maintenance carbonic acid gas/hydrocarbon), other reaction conditionss are identical with embodiment 1.
Embodiment 4: present embodiment and implementation column 1 difference are to use the ZSM-5 molecular sieve of K modification to be catalyzer, and maintenance carbonic acid gas/hydrocarbon is 3.0(mol/mol), other reaction conditionss are identical with embodiment 1.
Implementation column 5: the present embodiment difference from Example 1 is to use the ZSM-5 molecular sieve of Ba modification to be catalyzer, and maintenance carbonic acid gas/hydrocarbon is 4.0(mol/mol), other reaction conditionss are identical with embodiment 1.
Embodiment 6: the present embodiment difference from Example 1 is to use the MCM-22 molecular sieve of Ca modification to be catalyzer, and the carbon dioxide reaction pressure medium is 0.2MPa, and other reaction conditionss are identical with embodiment 1.
Embodiment 7: the present embodiment difference from Example 1 is to use the MCM-22 molecular sieve of Sr to be 0.5MPa as catalyzer, carbon dioxide reaction pressure medium, and other reaction conditionss are identical with embodiment 1.
Embodiment 8: the present embodiment difference from Example 1 is to use the MCM-22 molecular sieve of Cs to be 1.0MPa as catalyzer, carbon dioxide reaction pressure medium, and other reaction conditionss are identical with embodiment 1.
Embodiment 9: the present embodiment difference from Example 1 is to use the MCM-22 molecular sieve of K to be 1.2MPa as catalyzer, carbon dioxide reaction pressure medium, and other reaction conditionss are identical with embodiment 1.
Embodiment 10: the present embodiment difference from Example 1 is to use the X molecular sieve of Ba modification to be 1.5MPa as catalyzer, carbon dioxide reaction pressure medium, and other reaction conditionss are identical with embodiment 1.
Embodiment 11: present embodiment and embodiment one difference are that using the X molecular sieve of Ca is 380 ℃ as catalyzer, temperature of reaction, and other reaction conditionss are identical with embodiment 1.
Embodiment 12: the present embodiment difference from Example 1 is to use the X molecular sieve of Zn modification to be catalyzer, and temperature of reaction is 390 ℃, and other reaction conditionss are identical with embodiment 1.
Embodiment 13: the present embodiment difference from Example 1 is that using the X molecular sieve of Cs is 450 ℃ of lower reactions as catalyzer, maintenance toluene air speed, and other reaction conditionss are identical with embodiment 1.
Embodiment 14: the present embodiment difference from Example 1 is that using the X molecular sieve of K modification is 500 ℃ of lower reactions as catalyzer, maintenance toluene air speed, and other reaction conditionss are identical with embodiment 1.
Embodiment 15: the present embodiment difference from Example 1 is to use the X molecular sieve of Ba modification to be 1.0h as catalyzer, maintenance toluene air speed
-1Lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 16: the present embodiment difference from Example 1 is to use the Y molecular sieve of Ca to be 1.5h as catalyzer, maintenance toluene air speed
-1Lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 17: the present embodiment difference from Example 1 is to use the Y molecular sieve of Zn to be 2.0h as catalyzer, maintenance toluene air speed
-1Lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 18: the present embodiment difference from Example 1 is to use the Y molecular sieve of Cs to be 2.5h as catalyzer, maintenance toluene air speed
-1Lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 19: the present embodiment difference from Example 1 is to use the Y molecular sieve of K to be 3.0h as catalyzer, maintenance toluene air speed
-1Lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 20: the present embodiment difference from Example 1 is to use the Y molecular sieve of Bi modification to be 3.5h as catalyzer, maintenance toluene air speed
-1Lower reaction, other reaction conditionss are identical with embodiment 1.
Table 1 is catalyzed reaction result under above 13 kinds of embodiments.(form is too large, bad composing)
Catalyzed reaction result under 13 kinds of embodiments of table 1.
Claims (6)
1. the method for a highly selective methanol toluene side chain alkylation synthesizing styrene is characterized in that concrete steps are as follows:
On fixed-bed reactor, realize that by the alkaline molecular sieve catalyst that contains metal promoter toluene and methanol side chain alkylation come the method for synthesizing styrene; The mixture that forms take toluene and methyl alcohol is as raw material, and toluene and methyl alcohol mol ratio are 2.0:1 ~ 8.0:1, and maintenance toluene reaction velocity is 0.1 ~ 4 h
-1, under 350 ~ 540 ℃ temperature of reaction, reaction medium adopts carbonic acid gas, and control reaction medium pressure is 0.1～6.0MPa, and the mol ratio of carbonic acid gas and hydrocarbon is 0.5:1～10.0:1.
2. the method for highly selective methanol toluene side chain alkylation synthesizing styrene according to claim 1 is characterized in that reaction medium pressure is 0.1～2.0MPa, and the mol ratio of carbonic acid gas and hydrocarbon is 1.0:1～6.0:1.
3. the method for highly selective methanol toluene side chain alkylation synthesizing styrene according to claim 1 is characterized in that temperature of reaction is 400～500 ℃, and the toluene reaction velocity is 0.5～3.0h
-1
4. the method for highly selective methanol toluene side chain alkylation synthesizing styrene according to claim 1, the mol ratio that it is characterized in that toluene and methyl alcohol is 4.0:1～8.0:1.
5. the method for highly selective methanol toluene side chain alkylation synthesizing styrene according to claim 1 is characterized in that molecular sieve catalyst adopts zeolite molecular sieve, zeolite molecular sieve be in ZSM-5, MCM-22, X-type molecular sieve or the Y zeolite any.
6. the method for highly selective methanol toluene side chain alkylation synthesizing styrene according to claim 1, it is characterized in that it is 0.5 wt%～8 wt% of zeolite weight that described metal promoter adopts at least a among Ca, K, Zn, Cs, Sr, Bi or the Ba, metal promoter add-on.
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Cited By (7)
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|---|---|---|---|---|
| CN103288582A (en) * | 2013-06-04 | 2013-09-11 | 同济大学 | Method for improving the selectivity and reaction stability of arene prepared in methanol aromatization manner |
| CN106607070A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing ethylbenzene and styrene through side chain alkylation of toluene and methanol and application of catalyst |
| CN106607072A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing ethylbenzene and styrene by alkylating side chains of methylbenzene and methanol |
| CN109364990A (en) * | 2018-11-02 | 2019-02-22 | 太原理工大学 | A kind of preparation method and applications of KAPO catalyst |
| CN109847789A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | The method that bifunctional catalyst and preparation method thereof, toluene and methanol prepare styrene |
| CN110563539A (en) * | 2019-09-09 | 2019-12-13 | 内江师范学院 | Treatment process and equipment for high-concentration wastewater generated in production of styrene from methanol and toluene |
| CN111960910A (en) * | 2020-07-24 | 2020-11-20 | 浙江环化科技有限公司 | Method for preparing styrene by efficiently alkylating toluene and methanol side chains |
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| CN103288582A (en) * | 2013-06-04 | 2013-09-11 | 同济大学 | Method for improving the selectivity and reaction stability of arene prepared in methanol aromatization manner |
| CN106607070A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing ethylbenzene and styrene through side chain alkylation of toluene and methanol and application of catalyst |
| CN106607072A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing ethylbenzene and styrene by alkylating side chains of methylbenzene and methanol |
| CN106607070B (en) * | 2015-10-22 | 2019-04-12 | 中国石油化工股份有限公司 | For methylbenzene methanol side chain alkylation synthesizing ethyl benzene phenylethylene catalyst and application thereof |
| CN109847789A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | The method that bifunctional catalyst and preparation method thereof, toluene and methanol prepare styrene |
| CN109847789B (en) * | 2017-11-30 | 2021-03-02 | 中国科学院大连化学物理研究所 | Bifunctional catalyst and preparation method thereof, and method for preparing styrene from toluene and methanol |
| CN109364990A (en) * | 2018-11-02 | 2019-02-22 | 太原理工大学 | A kind of preparation method and applications of KAPO catalyst |
| CN109364990B (en) * | 2018-11-02 | 2021-06-04 | 太原理工大学 | Preparation method and application of KAPO catalyst |
| CN110563539A (en) * | 2019-09-09 | 2019-12-13 | 内江师范学院 | Treatment process and equipment for high-concentration wastewater generated in production of styrene from methanol and toluene |
| CN111960910A (en) * | 2020-07-24 | 2020-11-20 | 浙江环化科技有限公司 | Method for preparing styrene by efficiently alkylating toluene and methanol side chains |
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