CN102964203B - 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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- CN102964203B CN102964203B CN201210465997.9A CN201210465997A CN102964203B CN 102964203 B CN102964203 B CN 102964203B CN 201210465997 A CN201210465997 A CN 201210465997A CN 102964203 B CN102964203 B CN 102964203B
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- toluene
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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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- 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
The invention relates to a high-selectivity method for synthesizing styrene through methanol and toluene side chain alkylation. 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 0.1-4.0/h, the pressure of the reaction medium is 0.1-6.0MPa, and the molar ratio of carbon dioxide to hydrocarbon is 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, adopt under the reaction medium of carbonic acid gas, by molecular sieve catalyst, realize the novel method that toluene reacts with methanol alkylation high selectivity vinylbenzene continous-stable.
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, approximately more than 300 ten thousand tons of annual import volumes.And its main industrial mode of production-ethylbenzene dehydrogenation method synthesizing styrene at present, exist side reaction many, produce a large amount of greenhouse gases and the high problem of energy consumption.Adopt alkaline molecular sieve as catalyzer, by methylbenzene methanol side chain alkylation reaction synthesizing styrene, can effectively reduce energy consumption, reduce production cost, and can reduce the discharge 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 reaction product.Meanwhile, due to catalyzer, in methylbenzene methanol side chain alkylation reaction, to tie carbon serious, causes 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 alkylation of toluene methanol synthesizing styrene is is that on the molecular sieve catalyst of leading, soda acid concerted catalysis is reacted by alkalescence.For this methylbenzene methanol side chain alkylation reaction mechanism, basically identical viewpoint is: the generation that is first formaldehyde, formaldehyde is adsorbed by acid site, toluene and acid sites interact simultaneously, the activation of its pendant methyl Bei Jian center, then by carbanion mechanism generation side chain alkylation, react the vinylbenzene that generates ADSORPTION STATE with formaldehyde.
CH
3OH→HCHO+H
2
In above-mentioned this reaction process, because the hydrogen that the vinylbenzene generating can be taken off with methyl alcohol carries out addition reaction, generate ethylbenzene, selectivity of styrene and productive rate are reduced 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 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 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 first exchanged into H type molecular sieve by molecular sieve with ammonium salt, after roasting, with an alkali metal salt, exchange again, after dry, roasting, become alkaline molecular sieve, to be selected from B, P and be selected from least one the element dipping method in basic metal, alkaline-earth metal again, catalyzer is made in load, solved preferably that molecular sieve catalyst structure is easily destroyed 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 the problem that selectivity of styrene is low, reaction stability is poor existing in existing methylbenzene methanol side chain alkylation preparation of styrene technology simultaneously, 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. a 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, by alkaline molecular sieve catalyst, realize toluene and react new solution with the cinnamic continous-stable of methanol alkylation high selectivity.It adopts carbonic acid gas as reaction medium, using contain metal promoter modification molecular sieve as catalyzer, in high yield, prepare the cinnamic while, not only solve toluene and methanol alkylation and prepared the problem that selectivity of styrene is low, also effectively restrained and on catalyzer, tied the process that carbon causes inactivation, thereby also solved toluene and methanol alkylation is prepared 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, by the alkaline molecular sieve catalyst that contains metal promoter, realize the method that toluene and methanol side chain alkylation carry out synthesizing styrene; The mixture that toluene and methyl alcohol forms of take is 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 the temperature of reaction of 350 ~ 540 ℃, reaction medium adopts carbonic acid gas, and controlling 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.
In 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.
In the present invention, temperature of reaction is 400～500 ℃, and toluene reaction velocity is 0.5～3.0h
-1.
In the present invention, the mol ratio of toluene and methyl alcohol is 4.0:1～8.0:1.
In the present invention, molecular sieve catalyst adopt zeolite molecular sieve, zeolite molecular sieve be in ZSM-5, MCM-22, X-type molecular sieve or Y zeolite any.
In the present invention, described metal promoter adopts at least one in Ca, K, Zn, Cs, Sr, Bi or Ba, and metal promoter add-on is 0.5 wt%～8 wt% of zeolite weight.
Use toluene of the present invention and methanol alkylation to prepare vinylbenzene method, produce vinylbenzene productive rate high, and reaction stability is good, 500 hours obvious catalyst deactivation signs of nothing of successive reaction in fixed bed catalytic reactor.
In the present invention, the transformation efficiency of toluene and cinnamic optionally method of calculation are as follows:
The technical characterstic of the inventive method is using carbonic acid gas as a weak oxidant, utilize the redox generation carbon monoxide CO of carbonic acid gas and hydrogen and reacting 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 carbonic acid gas to generate reacting of carbon monoxide CO with the redox of tying carbon composition on catalyzer, effectively restrained the process that carbon causes inactivation of tying on 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 a difficult problem for stability and poor selectivity in existing toluene and methanol alkylation synthesizing styrene technique, make the catalyst stability of toluene and methanol alkylation synthesizing styrene and the requirement that selectivity of styrene has met industrial application preferably, there is good technology using value.
Embodiment
below by embodiment, further illustrate the present invention.
Embodiment 1: the reaction tubes bed bottom of the first miniature fixed bed catalytic reactor at internal diameter 1.5cm packs appropriate granulated glass sphere into, on granulated glass sphere, spread skim silica wool, pack the ZSM-5 molecular sieve catalyzer of the cylindric Ca modification of 3.0 ~ 5.0g into reaction tubes again, the upper strata appropriate granulated glass sphere that recharges, through temperature programming to 420 ℃ in 100 minutes, pass into carbonic acid gas, and pass into and consist of toluene and methanol=5(mol/mol with volume pump) reaction raw materials, keeping toluene mass space velocity is WHSV=1.0h
-1, keep carbonic acid gas/hydrocarbon=2(mol/mol), keeping reaction medium pressure is 0.3MPa, reaction stream fluid is got upper strata organism as product sample, through gas chromatographic analysis, calculates toluene conversion and the cinnamic selectivity of reaction.
Embodiment 2: it is 1(mol/mol as catalyzer, maintenance carbonic acid gas/hydrocarbon that this implementation column difference from Example 1 is to use the ZSM-5 molecular sieve of Zn modification), other reaction conditionss are identical with embodiment 1.
Embodiment 3: the ZSM-5 molecular sieve that the present embodiment difference from Example 1 is to use Cs modification for catalyzer, maintenance carbonic acid gas/hydrocarbon be 2.5(mol/mol), other reaction conditionss are identical with embodiment 1.
Embodiment 4: the present embodiment and implementation column 1 difference are that using the ZSM-5 molecular sieve of K modification is 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 that using the ZSM-5 molecular sieve of Ba modification is 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 that using the MCM-22 molecular sieve of Ca modification is catalyzer, and carbon dioxide reaction pressure medium is 0.2MPa, and other reaction conditionss are identical with embodiment 1.
Embodiment 7: the MCM-22 molecular sieve that the present embodiment difference from Example 1 is to use Sr for catalyzer, carbon dioxide reaction pressure medium be 0.5MPa, other reaction conditionss are identical with embodiment 1.
Embodiment 8: the MCM-22 molecular sieve that the present embodiment difference from Example 1 is to use Cs for catalyzer, carbon dioxide reaction pressure medium be 1.0MPa, other reaction conditionss are identical with embodiment 1.
Embodiment 9: the MCM-22 molecular sieve that present embodiment difference from Example 1 is to use K for catalyzer, carbon dioxide reaction pressure medium be 1.2MPa, other reaction conditionss are identical with embodiment 1.
Embodiment 10: the X molecular sieve that the present embodiment difference from Example 1 is to use Ba modification for catalyzer, carbon dioxide reaction pressure medium be 1.5MPa, other reaction conditionss are identical with embodiment 1.
Embodiment 11: the X molecular sieve that the present embodiment and embodiment one difference are to use Ca for catalyzer, temperature of reaction be 380 ℃, other reaction conditionss are identical with embodiment 1.
Embodiment 12: the present embodiment difference from Example 1 is that using the X molecular sieve of Zn modification is catalyzer, and temperature of reaction is 390 ℃, and other reaction conditionss are identical with embodiment 1.
Embodiment 13: the X molecular sieve that present embodiment difference from Example 1 is to use Cs for catalyzer, to keep toluene air speed be reaction at 450 ℃, other reaction conditionss are identical with embodiment 1.
Embodiment 14: the X molecular sieve that the present embodiment difference from Example 1 is to use K modification for catalyzer, to keep toluene air speed be reaction at 500 ℃, other reaction conditionss are identical with embodiment 1.
Embodiment 15: the X molecular sieve that the present embodiment difference from Example 1 is to use Ba modification for catalyzer, to keep toluene air speed be 1.0h
-1lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 16: the Y molecular sieve that the present embodiment difference from Example 1 is to use Ca for catalyzer, to keep toluene air speed be 1.5h
-1lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 17: the Y molecular sieve that the present embodiment difference from Example 1 is to use Zn for catalyzer, to keep toluene air speed be 2.0h
-1lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 18: the Y molecular sieve that the present embodiment difference from Example 1 is to use Cs for catalyzer, to keep toluene air speed be 2.5h
-1lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 19: the Y molecular sieve that the present embodiment difference from Example 1 is to use K for catalyzer, to keep toluene air speed be 3.0h
-1lower reaction, other reaction conditionss are identical with embodiment 1.
Embodiment 20: the Y molecular sieve that the present embodiment difference from Example 1 is to use Bi modification for catalyzer, to keep toluene air speed be 3.5h
-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 typesetting)
Catalyzed reaction result under 13 kinds of embodiments of table 1.
Claims (4)
1. a method for highly selective methanol toluene side chain alkylation synthesizing styrene, is characterized in that concrete steps are as follows:
On fixed-bed reactor, by the alkaline molecular sieve catalyst that contains metal promoter, realize the method that toluene and methanol side chain alkylation carry out synthesizing styrene; The mixture that toluene and methyl alcohol forms of take is 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 the temperature of reaction of 350 ~ 540 ℃, reaction medium adopts carbonic acid gas, and controlling reaction medium pressure is 0.1～6.0MPa, and the mol ratio of carbonic acid gas and toluene is 0.5:1～10.0:1; Described molecular sieve catalyst adopts zeolite molecular sieve, zeolite molecular sieve be in ZSM-5, MCM-22, X-type molecular sieve or Y zeolite any; Described metal promoter adopts at least one in Ca, K, Zn, Cs, Sr, Bi or Ba, and metal promoter add-on is 0.5 wt%～8 wt% of zeolite weight.
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 toluene 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 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.
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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 |
| CN106607072B (en) * | 2015-10-22 | 2019-10-11 | 中国石油化工股份有限公司 | The catalyst and application thereof of ethylbenzene and styrene is prepared for methylbenzene methanol side chain alkylation |
| 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 |
| 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 |
| 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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| CN101623649B (en) * | 2008-07-08 | 2011-08-17 | 中国石油化工股份有限公司 | Alkaline molecular sieve catalyst for preparing styrene |
| CN101623650B (en) * | 2008-07-08 | 2011-08-17 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst through toluene-methanol side chain alkylation |
| US8686205B2 (en) * | 2008-12-29 | 2014-04-01 | Fina Technology, Inc. | Method for production of styrene from toluene and methanol |
| IT1397885B1 (en) * | 2009-12-23 | 2013-02-04 | Polimeri Europa Spa | PROCESS FOR PREPARING ETHYLBENZENE. |
| TW201139336A (en) * | 2010-02-05 | 2011-11-16 | Fina Technology | Styrene production processes and catalysts for use therein |
| US8258359B2 (en) * | 2010-04-20 | 2012-09-04 | Fina Technology, Inc. | Alkylation of toluene to form styrene and ethylbenzene |
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