CN102649663B - There is the method for lower phenylacetylene selective hydrogenation in vinylbenzene - Google Patents
There is the method for lower phenylacetylene selective hydrogenation in vinylbenzene Download PDFInfo
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Abstract
The present invention relates to a kind of method that vinylbenzene exists lower phenylacetylene selective hydrogenation.Mainly solve in conventional art and there is the high technical problem of vinylbenzene rate of loss.The present invention is by adopting with the hydrocarbon fraction containing phenylacetylene for raw material, and temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material contacts with metal oxide catalyst, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, wherein, metal oxide catalyst comprises following component by weight percentage: the metallic nickel of (a) 2 ~ 50.0% or its oxide compound; (b) 0.05 ~ 10% be selected from least one element in rare earth or its oxide compound; C the technical scheme of the carrier of () 49 ~ 85%, solves this problem preferably, can be used for vinylbenzene and exist in the industrial production of lower hydrogenation removing phenylacetylene.
Description
Technical field
The present invention relates to a kind of method that vinylbenzene exists lower phenylacetylene selective hydrogenation, particularly about with the C8 hydrocarbon fraction containing phenylacetylene for raw material, the method for removing phenylacetylene.
Background technology
Vinylbenzene (ST) is the important monomer producing polystyrene (PS), ABS resin and styrene-butadiene rubber(SBR) etc.Its production method, based on ethylbenzene dehydrogenation method, in recent years, along with the development of ethylene industry and the maximization of scale, makes extracting and reclaiming vinylbenzene technology from pyrolysis gasoline become one of volume increase vinylbenzene technology received much concern.
Pyrolysis gasoline is the by-product of ethylene industry, output is about 60% ~ 70% of ethene production capacity, rich in styrene and xylol in C8 fraction wherein, a set of 1000kt/a ethylene unit, the vinylbenzene of 24 ~ 42kt/a can be obtained, recyclable xylol simultaneously, make cracking C8 fraction be upgraded to chemical values from fuel value, from pyrolysis gasoline, the cinnamic production cost of extracting and reclaiming is about 1/2 of dehydrogenation of ethylbenzene to styrene.
Cinnamic method is reclaimed from pyrolysis gasoline, generally believe it is possible that extractive distillation method at present, but, phenylacetylene (PA) is similar to cinnamic chemical structure, both are also similar to the interaction between extractive distillation solvent, therefore can not realize effectively being separated of vinylbenzene and PA by extracting rectifying.And the existence of PA, not only can increase catalyst consumption amount during anionic polymerization of styrene, affect chain length and polymerization velocity, and polystyrene performance depreciation can be caused, as variable color, degraded, spoiled and discharge smell etc.Therefore, exploitation highly selective Selective Hydrogenation Catalyst Phenylacetylene and technique become core and the key of pyrolysis gasoline extracting and reclaiming vinylbenzene technology.In addition, what need special concern is, carry out in phenylacetylene hydrogenation process under vinylbenzene exists, how reducing cinnamic loss is to greatest extent that in pyrolysis gasoline, whether extracting and reclaiming vinylbenzene possesses skills one of the key technical index of competitive power, cinnamic loss is lower, its Technical Economy is better, and technological competitiveness is stronger.
Patent CN1852877A, discloses a kind of method of phenylacetylene contaminant of reducing under styrene monomer exists.To the styrene monomer stream supply hydrogenation reactor of a small amount of phenylacetylene be comprised, also supply hydrogeneous hydrogenated gas.Styrene monomer stream is contacted with the beds comprising catalyzer with hydrogen, and described catalyzer is included in the copper compound of the reduction on θ alumina supporter.Hydrogenation reactor operates under 30psig pressure at least 60 DEG C of temperature with at least, and hydrogenation of phenylacetylene generates vinylbenzene.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 vinylbenzene exists rate of loss high (about about 3%).
Patent CN10878902A, disclose a kind of method and apparatus adopting hydride process to carry out the styrene monomer in purified styrene stream, it dilutes hydrogen by adopting hydrogen to add thinner such as nitrogen, discharge gas with ethylbenzene dehydrogenation and hydrogen is provided, reactor by multistage catalytic bed makes phenylacetylene contaminant hydrogenation be vinylbenzene, but only speak of lower concentration in this proprietary catalysts on the one hand if the selectivity of 300ppm phenylacetylene content is except alkynes method, simultaneously to phenylacetylene hydrogenation rate low (about 95%), it is high to there is loss in vinylbenzene.
In sum, mainly there is the high technical problem of vinylbenzene rate of loss in prior art, this brings larger difficulty to industrial practical application.
Summary of the invention
Technical problem to be solved by this invention is the technical problem that the vinylbenzene existed in previous literature exists that in lower phenylacetylene selective hydrogenation process, vinylbenzene rate of loss is high, provides a kind of new vinylbenzene to there is the method for lower phenylacetylene selective hydrogenation.The method has the low advantage of vinylbenzene rate of loss.
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 vinylbenzene exists the method for lower phenylacetylene selective hydrogenation, and with the hydrocarbon fraction containing phenylacetylene for raw material, temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, and reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material contacts with metal oxide catalyst, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, and wherein, metal oxide catalyst comprises following component by weight percentage:
The metallic nickel of (a) 2 ~ 50.0% or its oxide compound;
(b) 0.05 ~ 10% be selected from least one element in rare earth or its oxide compound;
(c) 0.01 ~ 6% be selected from IB, IIB, VIB or VIIB at least one element or its oxide compound in the periodic table of elements;
The carrier of (d) 49 ~ 85%.
In technique scheme, reaction conditions is preferably: temperature of reaction 25 ~ 80 DEG C, weight space velocity is 1 ~ 60 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 20: 1, and reaction pressure is 0 ~ 2.0MPa; By weight percentage, the consumption preferable range of metallic nickel or its oxide compound is 8.0 ~ 40.0% to metal oxide catalyst; The consumption preferable range being selected from least one element in rare earth or its oxide compound is 0.1 ~ 6.0%.Element in rare earth is preferably selected from least one in lanthanum, cerium or praseodymium; The consumption preferable range being selected from IB, IIB, VIB or VIIB at least one element or its oxide compound in the periodic table of elements is 0.1 ~ 4.0%; Be selected from IB, IIB, VIB or VIIB at least one element in the periodic table of elements and be preferably selected from least one in molybdenum, manganese, copper or zinc; Carrier is preferably selected from least one in aluminum oxide, silicon oxide or molecular sieve, is more preferably selected from aluminum oxide.
In technique scheme phenylacetylene hydrocarbon fraction in, by weight percentage, styrene content is 20 ~ 60%, and the content of phenylacetylene is 0.03 ~ 2%.
In this technology, vinylbenzene rate of loss calculation formula is: vinylbenzene quality × 100% in (in the vinylbenzene quality-product in raw material cinnamic quality)/raw material.
The preparation method of catalyzer of the present invention is: the solution impregnation cocatalyst component used in the nickel compound of carrier aequum and catalyzer be made into, and namely the carrier drying after dipping, in atmosphere 320 ~ 450 DEG C of roastings obtain oxidative catalyst finished product.Above-mentioned steps can be repeated and obtain required nickel content.Finished catalyst needs to use hydrogen reducing before use.
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 recycling vinyl benzene with pyrolysis gasoline technology, the added value of ethylbenzene is far below cinnamic added value, and meanwhile, the existence of micro-benzene acetylene is unfavorable to later separation, for this reason, how to maximize conversion phenylacetylene, avoid to greatest extent cinnamicly adding hydrogen loss, be the key reclaiming vinylbenzene technology simultaneously.We find in large quantity research, homemade nickel-base catalyst is adopted to carry out in phenylacetylene hydrogenation reaction process, there is good phenylacetylene hydrogenation selectivity, and dynamics research finds, nickel-base catalyst is adopted to carry out in phenylacetylene selective hydrogenation reaction process, phenylacetylene hydrogenation generates the activation energy of reaction activity far below styrene hydrogenation generation ethylbenzene reactions steps of vinylbenzene step, this transforms phenylacetylene for realizing maximizing, avoid to greatest extent cinnamicly adding hydrogen loss simultaneously, provide most important theories basis and theories integration from reaction kinetics angle.In addition, also find in research process, nickel-base catalyst, by adding auxiliary agent, modulation being carried out to activity, can further improve phenylacetylene hydrogenation selectivity, reducing cinnamic loss.
Adopt technical scheme of the present invention, with the hydrocarbon fraction containing phenylacetylene for raw material, adopt metallic nickel metal oxides to be catalyzer, temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material and catalyst exposure, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, and in reactor final effluent, the content of phenylacetylene preferably can reach 0, and vinylbenzene can reach free of losses, even part phenylacetylene hydrogenation is that vinylbenzene occurs that vinylbenzene increases (or vinylbenzene rate of loss is negative value), achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Take θ alumina supporter 20 grams, joining nickelous nitrate content is 12%, the content of lanthanum nitrate is 3%, and the content of zinc nitrate is in the solution of 1%, carries out equivalent impregnation, 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst A, makes nickel content be 8% of vehicle weight, lanthanum content is 0.2%, and the content of zinc is 0.2%.By above-mentioned obtained catalyzer hydrogen 300 DEG C of reduction 6 hours, then by weight percentage, containing 40% vinylbenzene, 10% ethylbenzene, carbon eight cut of 0.1% phenylacetylene is raw material, temperature of reaction 40 DEG C, weight space velocity 3 hours
-1, hydrogen/alkynes mol ratio is 2: 1, and reaction pressure is under the condition of 0.1MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0, and in reaction effluent, the content of phenylacetylene is 4ppm.
[embodiment 2]
Be carrier with gamma-alumina, according to condition and the method for embodiment 1, nickelous nitrate content is adopted to be the solution of 20% respectively, the content of lanthanum nitrate to be the solution of 6% and the content of zinc nitrate be 5% solution carry out equivalent impregnation method dipping, 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst B, make nickel content be 15% of vehicle weight, lanthanum content is 0.8%, and the content of zinc is 1%.With hydrogen temperature 400 DEG C activation 4 hours, then with containing 35% vinylbenzene, 12% ethylbenzene, carbon eight cut of 0.2% phenylacetylene is raw material, temperature of reaction 38 DEG C, and weight space velocity 0.4 hour
-1, hydrogen/alkynes mol ratio is 10: 1, and reaction pressure is under the condition of 2.5MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0.21%, phenylacetylene 1ppm in reaction effluent.
[embodiment 3]
Be carrier with gamma-alumina, according to condition and the method for embodiment 1, nickelous nitrate content is adopted to be the solution of 25% respectively, the content of lanthanum nitrate to be the solution of 10% and the content of cupric nitrate be 8% solution carry out equivalent impregnation method dipping, 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst C, make nickel content be 20% of vehicle weight, lanthanum content is 1.2%, and copper content is 4%.With hydrogen temperature 400 DEG C activation 4 hours, then by weight percentage, with containing 20% vinylbenzene, 15% ethylbenzene, carbon eight cut of 0.06% phenylacetylene is raw material, temperature of reaction 58 DEG C, and weight space velocity 15 hours
-1, hydrogen/alkynes mol ratio is 3: 1, and reaction pressure is under the condition of 0.5MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0.02%, and in reaction effluent, the content of phenylacetylene is 5ppm.
[embodiment 4]
With ZSM-5 molecular sieve (silica alumina ratio SiO
2/ Al
2o
3be 150) be carrier, according to condition and the method for embodiment 1, nickelous nitrate content is adopted to be the solution of 20% respectively, the content of praseodymium nitrate to be the solution of 6% and the content of nitric acid molybdenum be 3% solution carry out equivalent impregnation method dipping, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst D, make nickel content be 30% of vehicle weight, praseodymium content is 3%, and molybdenum content is 3%.By above-mentioned obtained catalyzer hydrogen 300 DEG C of reduction 6 hours, then by weight percentage, with containing 34% vinylbenzene, 8% ethylbenzene, carbon eight cut of 1.2% phenylacetylene is raw material, temperature of reaction 40 DEG C, and weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 30: 1, and reaction pressure is under the condition of 1.5MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is-0.5%, and in reaction effluent, the content of phenylacetylene is 6ppm.
[embodiment 5]
Be carrier with gamma-alumina, according to condition and the method for embodiment 1, adopt nickelous nitrate content to be the solution of 25% respectively, the content of cerous nitrate is 1%, and the content of manganous nitrate be 4% solution carry out equivalent impregnation method dipping, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst E, makes nickel content be 40% of vehicle weight, cerium content is 3%, and the content of manganese is 0.5%.With hydrogen temperature 400 DEG C activation 4 hours, then by weight percentage, with containing 56% vinylbenzene, 5% ethylbenzene, carbon eight cut of 2% phenylacetylene is raw material, temperature of reaction 85 DEG C, and weight space velocity 8 hours
-1, hydrogen/alkynes mol ratio is 4: 1, and reaction pressure is under the condition of 0.8MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0, and in reaction effluent, the content of phenylacetylene is 8ppm.
[embodiment 6]
With gamma-alumina is carrier, according to condition and the method for embodiment 1, adopt nickelous carbonate content to be the solution of 15% respectively, the content of cerous carbonate is 8%, and zinc nitrate content is equivalent impregnation method of the carrying out dipping of the solution of 6%, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst F, makes nickel content be 50% of vehicle weight, cerium content is 4%, and Zn content is 1%.With hydrogen temperature 350 DEG C activation 4 hours, then by weight percentage, with containing 26% vinylbenzene, 8% ethylbenzene, carbon eight cut of 0.06% phenylacetylene is raw material, temperature of reaction 55 DEG C, and weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 10: 1, and reaction pressure is under the condition of 1.5MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0.19%, and in reaction effluent, the content of phenylacetylene is 3ppm.
[embodiment 7]
With silicon oxide is carrier, according to condition and the method for embodiment 1, adopt nickel acetate content to be the solution of 12% respectively, and the content of lanthanum acetate is the solution of 2%, and the content of neutralized verdigris be 10% solution carry out equivalent impregnation method dipping, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst G, makes nickel content be 20% of vehicle weight, lanthanum content is 2%, and the content of copper is 3%.With hydrogen temperature 350 DEG C activation 4 hours, then by weight percentage, with containing 36% vinylbenzene, 5% ethylbenzene, carbon eight cut of 0.08% phenylacetylene is raw material, temperature of reaction 68 DEG C, and weight space velocity 6 hours
-1, hydrogen/alkynes mol ratio is 20: 1, and reaction pressure is under the condition of-0.04MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0.6%, and in reaction effluent, phenylacetylene is 6ppm.
[embodiment 8]
With gamma-alumina is carrier, according to condition and the method for embodiment 1, adopt that nickel acetate content is 12%, the content of lanthanum acetate is 1% respectively, the content of cerous nitrate is 2%, equivalent impregnation method dipping is carried out with the solution that the content of nitric acid molybdenum is 1%, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst H, nickel content is made to be 25% of vehicle weight, cerium content is 0.2%, and lanthanum content is 0.5%, and the content of molybdenum is 0.2%.With hydrogen temperature 350 DEG C activation 4 hours, then by weight percentage, with containing 36% vinylbenzene, 5% ethylbenzene, carbon eight cut of 0.08% phenylacetylene is raw material, temperature of reaction 68 DEG C, and weight space velocity 6 hours
-1, hydrogen/alkynes mol ratio is 20: 1, and reaction pressure is under the condition of-0.04MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0.1%, and in reaction effluent, the content of phenylacetylene is 7ppm.
[comparative example 1]
According to each step and the condition of embodiment 1, just there is no lanthanum nitrate in steeping fluid, obtained nickel-base catalyst I, nickel content is made to be 8% of vehicle weight, its reaction conditions and raw material are all identical, reaction result is: cinnamic rate of loss is 1.8%, and in reaction effluent, the content of phenylacetylene is 15ppm.
[comparative example 2]
According to each step and the condition of embodiment 2, just do not have lanthanum nitrate and zinc nitrate in steeping fluid, obtained nickel-base catalyst J, makes nickel content be 15% of vehicle weight.Other reaction conditions and raw material are all identical, and reaction result is: cinnamic rate of loss is 5.5%, and in reaction effluent, in reaction effluent, the content of phenylacetylene is 18ppm.
Claims (5)
1. there is a method for lower phenylacetylene selective hydrogenation in vinylbenzene, and with the hydrocarbon fraction containing phenylacetylene for raw material, temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, and reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material contacts with metal oxide catalyst, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, and wherein, metal oxide catalyst is composed of the following components by weight percentage:
The metallic nickel of (a) 2 ~ 50.0% or its oxide compound;
(b) 0.05 ~ 10% be selected from least one element in rare earth or its oxide compound;
(c) 0.01 ~ 6% be selected from IB, IIB, VIB or VIIB at least one element or its oxide compound in the periodic table of elements;
The carrier of (d) 49 ~ 85%.
2. there is the method for lower phenylacetylene selective hydrogenation in vinylbenzene according to claim 1, and it is characterized in that temperature of reaction 25 ~ 80 DEG C, weight space velocity is 1 ~ 60 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 20: 1, and reaction pressure is 0 ~ 2.0MPa; By weight percentage, the consumption of metallic nickel or its oxide compound is 8.0 ~ 40.0% to metal oxide catalyst; The consumption being selected from least one element in rare earth or its oxide compound is 0.1 ~ 6.0%; The consumption being selected from IB, IIB, VIB or VIIB at least one element or its oxide compound in the periodic table of elements is 0.1 ~ 4.0%.
3. there is the method for lower phenylacetylene selective hydrogenation in vinylbenzene according to claim 2, it is characterized in that the element be selected from rare earth is selected from least one in lanthanum, cerium or praseodymium; Be selected from IB, IIB, VIB or VIIB at least one element in the periodic table of elements and be selected from least one in molybdenum, manganese, copper or zinc; At least one in support selected from alumina, silicon oxide or molecular sieve.
4. there is the method for lower phenylacetylene selective hydrogenation according to vinylbenzene described in claim 3, it is characterized in that support selected from alumina.
5. there is the method for lower phenylacetylene selective hydrogenation according to vinylbenzene described in claim 1, it is characterized in that in the hydrocarbon fraction containing phenylacetylene, by weight percentage, styrene content is 20 ~ 60%, and the content of phenylacetylene is 0.03 ~ 2%.
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| CN107970949B (en) * | 2016-10-24 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of three selective hydrogenation catalyst of carbon, preparation method and method of hydrotreating |
| CN111285751B (en) * | 2018-12-10 | 2021-06-01 | 中国科学院化学研究所 | Method for preparing alkene compound from alkyne compound |
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| CN1798716A (en) * | 2003-06-04 | 2006-07-05 | 约翰森·马瑟公开有限公司 | Selective hydrogenation process and catalyst therefor |
| CN101475439A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Phenylacetylene selective hydrogenation method using compound bed in the presence of phenylethylene |
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| CN1798716A (en) * | 2003-06-04 | 2006-07-05 | 约翰森·马瑟公开有限公司 | Selective hydrogenation process and catalyst therefor |
| CN101475439A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Phenylacetylene selective hydrogenation method using compound bed in the presence of phenylethylene |
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