CN102649661A - Method for selectively hydrogenating phenylacetylene in presence of styrene - Google Patents
Method for selectively hydrogenating phenylacetylene in presence of styrene Download PDFInfo
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- CN102649661A CN102649661A CN2011100452397A CN201110045239A CN102649661A CN 102649661 A CN102649661 A CN 102649661A CN 2011100452397 A CN2011100452397 A CN 2011100452397A CN 201110045239 A CN201110045239 A CN 201110045239A CN 102649661 A CN102649661 A CN 102649661A
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Abstract
The invention relates to a method for selectively hydrogenating phenylacetylene in the presence of styrene. According to the method, the technical problem of high styrene loss rate in the prior art is mainly solved. The method comprises the following steps that with hydrocarbon fractions containing the phenylacetylene and alkane as diluent gas and under the conditions that the reaction temperature is 15-100DEG C, the weight space velocity is 0.01-100 hour<-1>, the mole ratio of hydrogen gas to the phenylacetylene is (1-30):1, the mol ratio of the raw materials to the alkane is (0.1-10):1 and the reaction pressure is -0.08MPa to 5.0MPa, the raw materials are contacted with metal oxides and the phenylacetylene in the reaction effluent is oxidized into the styrene, wherein the diluent gas alkane is selected from alkane compounds of C1-C4. According to the technical scheme, the problem is better solved. The method can be used for the industrial production of the removal of the phenylacetylene in the presence of the styrene by hydrogenating.
Description
Technical field
The present invention relates to a kind of vinylbenzene and exist phenylacetylene down to select the method for hydrogenation, particularly about to contain the C of phenylacetylene
8Hydrocarbon fraction is a raw material, the method for removing phenylacetylene.
Background technology
Vinylbenzene (ST) is the important monomer of producing PS (PS), ABS resin and styrene-butadiene rubber(SBR) etc.Its working method is main with the ethylbenzene dehydrogenation method, in recent years, along with the development of ethylene industry and the maximization of scale, makes that extracting recovery vinylbenzene technology becomes one of raising the output vinylbenzene technology that receives much concern from pyrolysis gasoline.
Pyrolysis gasoline is the by-product of ethylene industry, and output is about 60%～70% of ethene production capacity, rich in styrene and xylol in the C8 fraction wherein; One cover 1000kt/a ethylene unit; Can obtain the vinylbenzene of 24～42kt/a, recyclable xylol makes cracking C simultaneously
8Fraction is upgraded to chemistry from fuel value and is worth, and extracting is reclaimed cinnamic production cost and is about 1/2 of dehydrogenation of ethylbenzene to styrene from pyrolysis gasoline.
From pyrolysis gasoline, reclaim cinnamic method; Generally believe that at present feasible is the extractive distillation method; But; Therefore phenylacetylene (PA) is similar with cinnamic chemical structure, and both are also similar with the interaction between the extractive distillation solvent, can not realize effectively separating of vinylbenzene and PA through extracting rectifying.And the existence of PA, the catalyst consumption amount in the time of not only can increasing anionic polymerization of styrene influences chain length and polymerization velocity, and can cause the PS performance depreciation, like variable color, degraded, spoiled and discharge smell etc.Therefore, exploitation highly selective phenylacetylene selective hydrogenation catalyst and technology become core and the key that the vinylbenzene technology is reclaimed in the pyrolysis gasoline extracting.In addition; What need special concern is; In the presence of vinylbenzene, carry out in the phenylacetylene hydrogenation process, how to reduce cinnamic loss to greatest extent and be in the pyrolysis gasoline extracting and reclaim vinylbenzene one of the key of competitiveness technical indicator that whether possesses skills, cinnamic loss is low more; Its Technological Economy property is good more, and technological competitiveness is strong more.
Patent CN1852877A, disclose a kind of in the presence of styrene monomer the reduction phenylacetylene contaminant method.The styrene monomer stream that will comprise a small amount of phenylacetylene is supplied with hydrogenation reactor, also supplies with hydrogenous hydrogenated gas.Styrene monomer stream is contacted with the beds that comprises catalyzer with hydrogen, and said catalyst pack is contained in the reductive copper compound on the θ alumina supporter.Hydrogenation reactor is at least 60 ℃ of temperature and operate hydrogenation of phenylacetylene generation vinylbenzene at least under the 30psig pressure.Hydrogenated gas comprises the mixture of nitrogen and hydrogen, and this technology temperature of reaction is higher, and phenylacetylene hydrogenation rate low (about 70%) exists catalyst life shorter simultaneously, and there is rate of loss high (about about 3%) in vinylbenzene.
Patent CN10878902A; A kind of method and apparatus that adopts hydride process to come the styrene monomer in the purified styrene stream is disclosed; It dilutes hydrogen through adopting hydrogen adding thinner such as nitrogen; With the ethylbenzene dehydrogenation vent gas hydrogen is provided, making phenylacetylene contaminant hydrogenation by the reactor drum of multistage catalytic bed is vinylbenzene, but the selectivity of only speaking of lower concentration such as 300ppm phenylacetylene content in this patent catalyzer is on the one hand removed the alkynes method; To phenylacetylene hydrogenation rate low (about 95%), vinylbenzene exists rate of loss high simultaneously.
In sum, mainly there is the high technical problem of vinylbenzene rate of loss in prior art, and this uses industry practice and brings big difficulty.
Summary of the invention
Technical problem to be solved by this invention is that the vinylbenzene that in the past exists in the document exists down phenylacetylene to select the high technical problem of vinylbenzene rate of loss in the hydrogenation process, provides a kind of new vinylbenzene to exist phenylacetylene down to select the method for hydrogenation.This method has the low advantage of vinylbenzene rate of loss.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: there is the method for phenylacetylene selection hydrogenation down in a kind of vinylbenzene, is raw material with the hydrocarbon fraction that contains phenylacetylene, is carrier gas with alkane; 15～100 ℃ of temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/phenylacetylene mol ratio is 1～30: 1, hydrogen/alkane mol ratio is 0.1～10: 1; Reaction pressure is under the condition of-0.08～5.0MPa, and raw material contacts with metal oxide catalyst, and phenylacetylene is hydrogenated and is vinylbenzene in the reaction effluent; Wherein, alkane is selected from C
1～C
4Alkane compound.
Reaction conditions is preferably in the technique scheme: 25～80 ℃ of temperature of reaction, weight space velocity are 1～60 hour
-1, hydrogen/phenylacetylene mol ratio is 1～20: 1, and hydrogen/alkane mol ratio is 0.2～8: 1, and reaction pressure is 0～2.0MPa; The metal oxide catalyst active ingredient is preferably selected from least a in metallic nickel or the palladium metal; When preferable alloy nickel was catalyzer, its content counted 10～50% with catalyst weight per-cent; When the preferable alloy palladium was catalyzer, its content counted 0.1～3% with catalyst weight per-cent.
Carrier gas alkane is preferably selected from least a in methane, ethane or the propane in the technique scheme.In the hydrocarbon fraction of phenylacetylene, by weight percentage, styrene content is 20～60%, and the content of phenylacetylene is 0.03～2%.
In the present technique, vinylbenzene rate of loss calculation formula is: vinylbenzene quality * 100% in (cinnamic quality in the vinylbenzene quality-product in the raw material)/raw material.
As everyone knows, the hydrogenation reaction of phenylacetylene is a typical cascade reaction, and intermediate product is vinylbenzene; If excessive hydrogenation can generate ethylbenzene, and in the recycling vinyl benzene with pyrolysis gasoline technology, the added value of ethylbenzene is far below cinnamic added value; Simultaneously, the existence of micro-benzene acetylene is unfavorable to later separation, for this reason; How maximizing the conversion phenylacetylene, avoid the cinnamic hydrogen loss that adds to greatest extent simultaneously, is the key that reclaims the vinylbenzene technology.We find in big quantity research; Adopt nickel-base catalyst to carry out in the phenylacetylene selective hydrogenation reaction process; The phenylacetylene hydrogenation generates the activation energy of the reaction activity of vinylbenzene step far below vinylbenzene hydrogenation generation ethylbenzene reactions step; This transforms phenylacetylene for realizing maximization, avoids the cinnamic hydrogen loss that adds simultaneously to greatest extent, provides the most important theories basis to support with theoretical from the reaction kinetics angle.In addition; Find in the research process, in the presence of certain carrier gas, in the phenylacetylene hydrogenation process; Cinnamic rate of loss can reduce; This is because the existence of carrier gas has reduced the partial concn of hydrogen, and then the phenylacetylene hydrogenation that can avoid causing because of the hydrogen partial concn is too high excessively causes the generation of low value-added ethylbenzene.For diluents, C
1～C
4Alkane compound, especially at least a effect in methane, ethane or the propane is better.
Adopting technical scheme of the present invention, is raw material with the hydrocarbon fraction that contains phenylacetylene, with C
1～C
4Alkane compound be carrier gas, adopting metallic nickel or palladium metal oxide compound is catalyzer, is 15～100 ℃ in temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/phenylacetylene mol ratio is 1～30: 1, hydrogen/alkane mol ratio is 0.1～10: 1; Reaction pressure is under the condition of-0.08～5.0MPa, and raw material contacts with metal oxide catalyst, and phenylacetylene is hydrogenated and is vinylbenzene in the reaction effluent; The content of phenylacetylene preferably can reach 0 in the reactor drum final effluent; Vinylbenzene can reach free of losses, even the part phenylacetylene is hydrogenated to vinylbenzene and vinylbenzene occurs and increase (or the vinylbenzene rate of loss is a negative value), has obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Use the θ aluminum oxide to be carrier, using load method to prepare charge capacity is 13% nickel catalyzator precursor 10 grams, before using with hydrogen in 400 ℃ of activation of temperature after 4 hours; Obtain nickel catalyzator, by weight percentage, contain 40% vinylbenzene; 10% ethylbenzene, carbon eight cuts of 0.1% phenylacetylene are raw material, are carrier gas with methane; 45 ℃ of temperature of reaction, weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 2: 1, hydrogen/methane mol ratio is 0.5: 1; Reaction pressure is under the condition of 0.2MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts; Reaction result is: cinnamic rate of loss is 0.15%, and the content of phenylacetylene is 2ppm in the reaction effluent.
[embodiment 2]
Use the θ aluminum oxide to be carrier, using load method to prepare charge capacity is 45% nickel catalyzator precursor 10 grams, before using with hydrogen 400 ℃ of activation of temperature 4 hours; With containing 35% vinylbenzene; 12% ethylbenzene, carbon eight cuts of 0.2% phenylacetylene are raw material, are carrier gas with methane; 38 ℃ of temperature of reaction, weight space velocity 0.4 hour
-1, hydrogen/alkynes mol ratio is 10: 1, hydrogen/methane mol ratio is 0.8: 1; Reaction pressure is under the condition of 2.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts; Reaction result is: cinnamic rate of loss is 0.1%, and phenylacetylene can't check in the reaction effluent.
[embodiment 3]
Use gamma-alumina to be carrier, using load method to prepare charge capacity is 20% nickel catalyzator precursor 10 grams, before using with hydrogen 400 ℃ of activation of temperature 4 hours; With methane is carrier gas, by weight percentage, and with containing 20% vinylbenzene; 15% ethylbenzene; Carbon eight cuts of 0.06% phenylacetylene are raw material, 58 ℃ of temperature of reaction, and weight space velocity 15 hours
-1, hydrogen/alkynes mol ratio is 3: 1, hydrogen/methane mol ratio is 1: 1; Reaction pressure is under the condition of 0.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts; Reaction result is: cinnamic rate of loss is 0.08%, and the content of phenylacetylene is 4ppm in the reaction effluent.
[embodiment 4]
Use the ZSM-5 molecular sieve to be carrier, using load method to prepare charge capacity is 30% nickel catalyzator precursor 10 grams, before using with hydrogen 400 ℃ of activation of temperature 4 hours; With ethane is carrier gas, by weight percentage, and with containing 34% vinylbenzene; 8% ethylbenzene; Carbon eight cuts of 1.2% phenylacetylene are raw material, 40 ℃ of temperature of reaction, and weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 30: 1, hydrogen/ethane mol ratio is 2: 1; Reaction pressure is under the condition of 1.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts; Reaction result is: cinnamic rate of loss is-0.6%, and the content of phenylacetylene is 1ppm in the reaction effluent.
[embodiment 5]
Use the mixture of γ and αYang Hualv to be carrier, using load method to prepare charge capacity is 25% nickel catalyzator precursor 10 grams, before using with hydrogen 400 ℃ of activation of temperature 4 hours; Employing propane is carrier gas, by weight percentage, and with containing 56% vinylbenzene; 5% ethylbenzene; Carbon eight cuts of 2% phenylacetylene are raw material, 85 ℃ of temperature of reaction, and weight space velocity 8 hours
-1, hydrogen/alkynes mol ratio is 4: 1, hydrogen/propane mol ratio is 4: 1; Reaction pressure is under the condition of 0.8MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts; Reaction result is: cinnamic rate of loss is-0.8%, and the content of phenylacetylene is 2ppm in the reaction effluent.
[embodiment 6]
Use the mixture of gamma-alumina to be carrier, using load method to prepare charge capacity is 0.5% palladium catalyst precursor 10 grams, before using with hydrogen 350 ℃ of activation of temperature 4 hours; The employing butane is a carrier gas, by weight percentage, and with containing 26% vinylbenzene; 8% ethylbenzene; Carbon eight cuts of 0.06% phenylacetylene are raw material, 55 ℃ of temperature of reaction, and weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 10: 1, hydrogen/propane mol ratio is 8: 1; Reaction pressure is under the condition of 1.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts; Reaction result is: cinnamic rate of loss is 0.2%, and the content of phenylacetylene is 12ppm in the reaction effluent.
[embodiment 7]
Use the mixture of gamma-alumina to be carrier, using load method to prepare charge capacity is 3% palladium catalyst precursor 10 grams, before using with hydrogen 350 ℃ of activation of temperature 4 hours; Employing methane is carrier gas, by weight percentage, and with containing 36% vinylbenzene; 5% ethylbenzene; Carbon eight cuts of 0.08% phenylacetylene are raw material, 68 ℃ of temperature of reaction, and weight space velocity 6 hours
-1, hydrogen/alkynes mol ratio is 20: 1, hydrogen/methane mol ratio is 1: 1; Reaction pressure is-condition of 0.04MPa under, adopt fixed-bed reactor that raw material is contacted with catalyzer, react; Reaction result is: cinnamic rate of loss is 0.05%, and phenylacetylene can't check in the reaction effluent.
[embodiment 8]
Use the mixture of gamma-alumina to be carrier, using load method to prepare charge capacity is 3% palladium catalyst precursor 10 grams, before using with hydrogen 350 ℃ of activation of temperature 4 hours; Employing methane and ethane mol ratio are that 1: 1 gas mixture is a carrier gas, by weight percentage, and with containing 36% vinylbenzene; 5% ethylbenzene; Carbon eight cuts of 0.08% phenylacetylene are raw material, 68 ℃ of temperature of reaction, and weight space velocity 6 hours
-1Hydrogen/alkynes mol ratio is 20: 1, and hydrogen/(methane and ethane) mol ratio is 1: 1, reaction pressure is-condition of 0.04MPa under; Adopt fixed-bed reactor that raw material is contacted with catalyzer; React, reaction result is: cinnamic rate of loss is 0.03%, and phenylacetylene can't check in the reaction effluent.
[comparative example 1]
Each step and condition according to embodiment 1 just do not have diluents, and other condition and raw material are all identical, and reaction result is: cinnamic rate of loss is 1%, and the content of phenylacetylene is 0.5ppm in the reaction effluent.
[comparative example 2]
Each step and condition according to embodiment 6 just do not have diluents, and other condition and raw material are all identical, and reaction result is: cinnamic rate of loss is 2%, and phenylacetylene can't check in the reaction effluent.
Claims (5)
1. there is the method for phenylacetylene selection hydrogenation down in a vinylbenzene, is raw material with the hydrocarbon fraction that contains phenylacetylene, is carrier gas with alkane, and 15～100 ℃ of temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/phenylacetylene mol ratio is 1～30: 1, hydrogen/alkane mol ratio is 0.1～10: 1; Reaction pressure is under the condition of-0.08～5.0MPa, and raw material contacts with metal oxide catalyst, and phenylacetylene is hydrogenated and is vinylbenzene in the reaction effluent; Wherein, carrier gas alkane is selected from C
1～C
4Alkane compound.
2. have the method for phenylacetylene selection hydrogenation down according to the said vinylbenzene of claim 1, it is characterized in that 25～80 ℃ of temperature of reaction, weight space velocity is 1～60 hour
-1, hydrogen/phenylacetylene mol ratio is 1～20: 1, and hydrogen/alkane mol ratio is 0.2～8: 1, and reaction pressure is 0～2.0MPa; The metal oxide catalyst active ingredient is selected from least a in metallic nickel or the palladium metal.
3. have the method for phenylacetylene selection hydrogenation down according to the said vinylbenzene of claim 2, it is characterized in that the catalyst activity component is a nickel, its content counts 10～50% with catalyst weight per-cent; The catalyst activity component is a palladium, and its content counts 0.1～3% with catalyst weight per-cent.
4. exist phenylacetylene down to select the method for hydrogenation according to the said vinylbenzene of claim 1, it is characterized in that alkane is selected from least a in methane, ethane or the propane.
5. have the method for phenylacetylene selection hydrogenation down according to the said vinylbenzene of claim 1, it is characterized in that containing in the hydrocarbon fraction of phenylacetylene, by weight percentage, styrene content is 20～60%, and the content of phenylacetylene is 0.03～2%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107954814A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The method of phenylacetylene selection hydrogenation in eight fraction of carbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384085A (en) * | 2001-05-07 | 2002-12-11 | 弗纳技术股份有限公司 | Method and system of purifying styrene material with catalyst containing small amount of palladium |
| CN101475438A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Selective hydrogenation method for phenylacetylene in the presence of phenylethylene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384085A (en) * | 2001-05-07 | 2002-12-11 | 弗纳技术股份有限公司 | Method and system of purifying styrene material with catalyst containing small amount of palladium |
| CN101475438A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Selective hydrogenation method for phenylacetylene in the presence of phenylethylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107954814A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The method of phenylacetylene selection hydrogenation in eight fraction of carbon |
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Application publication date: 20120829 |