CN102649663A - Method for removing phenylacetylene through selective hydrogenation in presence of styrene - Google Patents
Method for removing phenylacetylene through selective hydrogenation in presence of styrene Download PDFInfo
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- CN102649663A CN102649663A CN2011100453027A CN201110045302A CN102649663A CN 102649663 A CN102649663 A CN 102649663A CN 2011100453027 A CN2011100453027 A CN 2011100453027A CN 201110045302 A CN201110045302 A CN 201110045302A CN 102649663 A CN102649663 A CN 102649663A
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- phenylacetylene
- vinylbenzene
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- styrene
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- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 title claims abstract description 148
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- -1 by weight percentage Natural products 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910000480 nickel oxide Inorganic materials 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 28
- 229910052759 nickel Inorganic materials 0.000 description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 150000001345 alkine derivatives Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for removing phenylacetylene through selective hydrogenation in the presence of styrene, and mainly solves the technical problem of high loss rate of styrene in the prior art. Through the adoption of the technical scheme that hydrocarbon fractions containing phenylacetylene are taken as raw materials, and under the conditions that the reaction temperature is 15 to 100 DEG C, the weight space velocity is 0.01 to 100 hours <-1>, the mol ratio of hydrogen to phenylacetylene is (1 to 30) : 1, and the reaction pressure is -0.08 to 5.0 MPa, the raw materials are in contact with a metal oxide catalyst, and phenylacetylene in a reaction effluent is hydrogenated to form styrene, wherein the metal oxide catalyst comprises the following components in percent by weight: (a) 2 to 50.0 percent of metallic nickel oxide or other oxides, (b) 0.05 to 10 percent of at least one rare earth element oxide or other oxides, and (c) 49 to 85 percent of carrier, the invention solves the problem well, and can be used in the industrial production of removing phenylacetylene in the presence of styrene.
Description
Technical field
The present invention relates to a kind of vinylbenzene and have the method for phenylacetylene selective hydrogenation down, particularly about being raw material with the C8 hydrocarbon fraction that contains phenylacetylene, 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; Output is about 60%～70% of ethene production capacity, rich in styrene and xylol in the C8 fraction wherein, a cover 1000kt/a ethylene unit; Can obtain the vinylbenzene of 24～42kt/a; Simultaneously recyclable xylol makes cracking C8 fraction be 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 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 the high technical problem of vinylbenzene rate of loss in the phenylacetylene selective hydrogenation process, provides a kind of new vinylbenzene to have the method for phenylacetylene selective hydrogenation down.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 selective hydrogenation down in a kind of vinylbenzene, is raw material with the hydrocarbon fraction that contains phenylacetylene, and 15～100 ℃ of temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/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; Phenylacetylene is hydrogenated and is vinylbenzene in the reaction effluent, and wherein, metal oxide catalyst comprises following component by weight percentage:
(a) 2～50.0% metallic nickel or its oxide compound;
(b) 0.05～10% be selected from least a element or its oxide compound in the rare earth;
(c) 0.01～6% be selected from least a element of IB in the periodic table of elements, IIB, VIB or VIIB or its oxide compound;
(d) 49～85% carrier.
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, reaction pressure is 0～2.0MPa; Metal oxide catalyst by weight percentage, the consumption preferable range of metallic nickel or its oxide compound is 8.0～40.0%; At least a element or the consumption preferable range of its oxide compound that are selected from the rare earth are 0.1～6.0%.Element in the rare earth is preferably selected from lanthanum, cerium or the praseodymium at least a; The consumption preferable range that is selected from least a element of IB in the periodic table of elements, IIB, VIB or VIIB or its oxide compound is 0.1～4.0%; Being selected from least a element of IB in the periodic table of elements, IIB, VIB or VIIB is preferably selected from molybdenum, manganese, copper or the zinc at least a; Carrier is preferably selected from aluminum oxide, silicon oxide or the molecular sieve at least a, more preferably is selected from aluminum oxide.
In the hydrocarbon fraction of phenylacetylene, by weight percentage, styrene content is 20～60% in the technique scheme, 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.
Preparation of catalysts method of the present invention is: with the solution impregnation that carrier is made into the cocatalyst component of using in the nickel compound of aequum and the catalyzer, soaked carrier through dry, 320～450 ℃ of roastings promptly get the oxidative catalyst finished product in air.Can repeat above-mentioned steps and make required nickel content.Finished catalyst need be used 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 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 homemade nickel-base catalyst in carrying out the phenylacetylene hydrogenation process; Have phenylacetylene hydrogenation selectivity preferably, and dynamics research is found, adopted 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 also in the research process that nickel-base catalyst carries out modulation through adding auxiliary agent to activity, can further improve the phenylacetylene hydrogenation selectivity, reduces cinnamic loss.
Adopting technical scheme of the present invention, is raw material with the hydrocarbon fraction that contains phenylacetylene, and adopting metallic nickel Base Metal oxide compound is catalyzer, and 15～100 ℃ of temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/phenylacetylene mol ratio is 1～30: 1, reaction pressure is under the condition of-0.08～5.0MPa; Raw material contacts with catalyzer; Phenylacetylene is hydrogenated and is vinylbenzene in the reaction effluent, and the content of phenylacetylene preferably can reach 0 in the reactor drum final effluent, and 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), 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]
Take by weighing θ alumina supporter 20 grams, joining nickelous nitrate content is 12%, and the content of Lanthanum trinitrate is 3%; The content of zinc nitrate was in 1% the solution, to carry out equivalent impregnation, 120 ℃ of dryings 6 hours; 400 ℃ of roastings 8 hours make nickel-base catalyst A, make that nickel content is 8% of vehicle weight; Lanthanum content is 0.2%, and the content of zinc is 0.2%.The above-mentioned catalyzer that makes was reduced 6 hours at 300 ℃ with hydrogen, then by weight percentage, contain 40% vinylbenzene, 10% ethylbenzene, carbon eight cuts of 0.1% phenylacetylene are raw material, 40 ℃ of temperature of reaction, weight space velocity 3 hours
-1, hydrogen/alkynes mol ratio is 2: 1, and reaction pressure is under the condition of 0.1MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts, and reaction result is: cinnamic rate of loss is 0, and the content of phenylacetylene is 4ppm in the reaction effluent.
[embodiment 2]
Use gamma-alumina to be carrier, according to condition and the method for embodiment 1, adopting nickelous nitrate content respectively is 20% solution; The content of Lanthanum trinitrate is that the content of 6% solution and zinc nitrate is that 5% solution carries out equivalent impregnation method dipping, 120 ℃ of dryings 6 hours, and 400 ℃ of roastings 8 hours; Make nickel-base catalyst B; Make that nickel content is 15% of vehicle weight, lanthanum content is 0.8%, and the content of zinc is 1%.With hydrogen 400 ℃ of activation of temperature 4 hours, then with containing 35% vinylbenzene, 12% ethylbenzene, carbon eight cuts of 0.2% phenylacetylene are raw material, 38 ℃ of temperature of reaction, weight space velocity 0.4 hour
-1, hydrogen/alkynes mol ratio is 10: 1, and reaction pressure is under the condition of 2.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts, and reaction result is: cinnamic rate of loss is 0.21%, phenylacetylene 1ppm in the reaction effluent.
[embodiment 3]
Use gamma-alumina to be carrier, according to condition and the method for embodiment 1, adopting nickelous nitrate content respectively is 25% solution; The content of Lanthanum trinitrate is that the content of 10% solution and cupric nitrate is that 8% solution carries out equivalent impregnation method dipping, 120 ℃ of dryings 6 hours, and 400 ℃ of roastings 8 hours; Make nickel-base catalyst C; Make that nickel content is 20% of vehicle weight, lanthanum content is 1.2%, and copper content is 4%.With hydrogen 400 ℃ of activation of temperature 4 hours, then by weight percentage, with containing 20% vinylbenzene, 15% ethylbenzene, carbon eight cuts of 0.06% phenylacetylene are raw material, 58 ℃ of temperature of reaction, weight space velocity 15 hours
-1, hydrogen/alkynes mol ratio is 3: 1, and reaction pressure is under the condition of 0.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts, and reaction result is: cinnamic rate of loss is 0.02%, and the content of phenylacetylene is 5ppm in the reaction effluent.
[embodiment 4]
With ZSM-5 molecular sieve (silica alumina ratio SiO
2/ Al
2O
3Be 150) for carrier, according to condition and the method for embodiment 1, adopting nickelous nitrate content respectively is 20% solution; The content of praseodymium nitrate is that the content of 6% solution and nitric acid molybdenum is that 3% solution carries out equivalent impregnation method dipping, then 120 ℃ of dryings 6 hours, and 400 ℃ of roastings 8 hours; Make nickel-base catalyst D; Make that nickel content is 30% of vehicle weight, praseodymium content is 3%, and molybdenum content is 3%.With the above-mentioned catalyzer that makes with hydrogen 300 ℃ of reduction 6 hours, then by weight percentage, with containing 34% vinylbenzene, 8% ethylbenzene, carbon eight cuts of 1.2% phenylacetylene are raw material, 40 ℃ of temperature of reaction, weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 30: 1, and reaction pressure is under the condition of 1.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts, and reaction result is: cinnamic rate of loss is-0.5%, and the content of phenylacetylene is 6ppm in the reaction effluent.
[embodiment 5]
Use gamma-alumina to be carrier, according to condition and the method for embodiment 1, adopting nickelous nitrate content respectively is 25% solution; The content of cerous nitrate be 1% and the content of manganous nitrate be that 4% solution carries out equivalent impregnation method dipping, then 120 ℃ of dryings 6 hours; 400 ℃ of roastings 8 hours make nickel-base catalyst E, make that nickel content is 40% of vehicle weight; Cerium content is 3%, and the content of manganese is 0.5%.With hydrogen 400 ℃ of activation of temperature 4 hours, then by weight percentage, with containing 56% vinylbenzene, 5% ethylbenzene, carbon eight cuts of 2% phenylacetylene are raw material, 85 ℃ of temperature of reaction, weight space velocity 8 hours
-1, hydrogen/alkynes mol ratio is 4: 1, and reaction pressure is under the condition of 0.8MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts, and reaction result is: cinnamic rate of loss is 0, and the content of phenylacetylene is 8ppm in the reaction effluent.
[embodiment 6]
Use the carrier that is of gamma-alumina, according to condition and the method for embodiment 1, adopting nickelous carbonate content respectively is 15% solution; The content of cerous carbonate be 8% and zinc nitrate content be the equivalent impregnation method of the carrying out dipping of 6% solution, then 120 ℃ of dryings 6 hours; 400 ℃ of roastings 8 hours make nickel-base catalyst F, make that nickel content is 50% of vehicle weight; Cerium content is 4%, and zinc content is 1%.With hydrogen 350 ℃ of activation of temperature 4 hours, then by weight percentage, with containing 26% vinylbenzene, 8% ethylbenzene, carbon eight cuts of 0.06% phenylacetylene are raw material, 55 ℃ of temperature of reaction, weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 10: 1, and reaction pressure is under the condition of 1.5MPa, adopts fixed-bed reactor that raw material is contacted with catalyzer, reacts, and reaction result is: cinnamic rate of loss is 0.19%, and the content of phenylacetylene is 3ppm in the reaction effluent.
[embodiment 7]
Use the carrier that is of silicon oxide, according to condition and the method for embodiment 1, adopting nickel acetate content respectively is 12% solution; With the content of lanthanum acetate be that the content of 2% solution and neutralized verdigris is that 10% solution carries out equivalent impregnation method dipping, then 120 ℃ of dryings 6 hours; 400 ℃ of roastings 8 hours make nickel-base catalyst G, make that nickel content is 20% of vehicle weight; Lanthanum content is 2%, and the content of copper is 3%.With hydrogen 350 ℃ of activation of temperature 4 hours, then by weight percentage, with containing 36% vinylbenzene, 5% ethylbenzene, carbon eight cuts of 0.08% phenylacetylene are raw material, 68 ℃ of temperature of reaction, weight space velocity 6 hours
-1, hydrogen/alkynes mol ratio is 20: 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 0.6%, phenylacetylene is 6ppm in the reaction effluent.
[embodiment 8]
Use the carrier that is of gamma-alumina,, adopt respectively that nickel acetate content is 12%, the content of lanthanum acetate is 1% according to condition and the method for embodiment 1; The content of cerous nitrate be 2% and the content of nitric acid molybdenum be that 1% solution carries out equivalent impregnation method dipping, then 120 ℃ of dryings 6 hours; 400 ℃ of roastings 8 hours make nickel-base catalyst H, make that nickel content is 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 350 ℃ of activation of temperature 4 hours, then by weight percentage, with containing 36% vinylbenzene, 5% ethylbenzene, carbon eight cuts of 0.08% phenylacetylene are raw material, 68 ℃ of temperature of reaction, weight space velocity 6 hours
-1, hydrogen/alkynes mol ratio is 20: 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 0.1%, the content of phenylacetylene is 7ppm in the reaction effluent.
[comparative example 1]
Each step and condition according to embodiment 1; Just there is not Lanthanum trinitrate in the steeping fluid; Make nickel-base catalyst I, make that nickel content is 8% of vehicle weight, its reaction conditions and raw material are all identical; Reaction result is: cinnamic rate of loss is 1.8%, and the content of phenylacetylene is 15ppm in the reaction effluent.
[comparative example 2]
According to each step and the condition of embodiment 2, just there are not Lanthanum trinitrate and zinc nitrate in the steeping fluid, make nickel-base catalyst J, make that nickel content is 15% of vehicle weight.Other reaction conditions and raw material are all identical, and reaction result is: cinnamic rate of loss is 5.5%, in the reaction effluent in the reaction effluent content of phenylacetylene be 18ppm.
Claims (5)
1. there is the method for phenylacetylene selective hydrogenation down in a vinylbenzene, is raw material with the hydrocarbon fraction that contains phenylacetylene, and 15～100 ℃ of temperature of reaction, weight space velocity is 0.01～100 hour
-1, hydrogen/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; Phenylacetylene is hydrogenated and is vinylbenzene in the reaction effluent, and wherein, metal oxide catalyst comprises following component by weight percentage:
(a) 2～50.0% metallic nickel or its oxide compound;
(b) 0.05～10% be selected from least a element or its oxide compound in the rare earth;
(c) 0.01～6% be selected from least a element of IB in the periodic table of elements, IIB, VIB or VIIB or its oxide compound;
(d) 49～85% carrier.
2. have the method for phenylacetylene selective 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, reaction pressure is 0～2.0MPa; Metal oxide catalyst by weight percentage, the consumption of metallic nickel or its oxide compound is 8.0～40.0%; At least a element or the consumption of its oxide compound that are selected from the rare earth are 0.1～6.0%; The consumption that is selected from least a element of IB in the periodic table of elements, IIB, VIB or VIIB or its oxide compound is 0.1～4.0%.
3. have the method for phenylacetylene selective hydrogenation down according to the said vinylbenzene of claim 2, the element that it is characterized in that being selected from the rare earth is selected from lanthanum, cerium or the praseodymium at least a; Being selected from least a element of IB in the periodic table of elements, IIB, VIB or VIIB is selected from molybdenum, manganese, copper or the zinc at least a; Carrier is selected from aluminum oxide, silicon oxide or the molecular sieve at least a.
4. there is the method for phenylacetylene selective hydrogenation down according to the said vinylbenzene of claim 3, it is characterized in that carrier is selected from aluminum oxide.
5. have the method for phenylacetylene selective 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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| CN107970949A (en) * | 2016-10-24 | 2018-05-01 | 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 |
| CN107970933A (en) * | 2016-10-24 | 2018-05-01 | 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 |
| CN111285751A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院化学研究所 | A kind of 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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| CN107970949A (en) * | 2016-10-24 | 2018-05-01 | 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 |
| CN107970933A (en) * | 2016-10-24 | 2018-05-01 | 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 |
| CN107970933B (en) * | 2016-10-24 | 2019-12-24 | 中国石油化工股份有限公司 | Carbon-three selective hydrogenation catalyst, preparation method and hydrogenation method |
| CN111285751A (en) * | 2018-12-10 | 2020-06-16 | 中国科学院化学研究所 | A kind of method for preparing alkene compound from alkyne compound |
| CN111285751B (en) * | 2018-12-10 | 2021-06-01 | 中国科学院化学研究所 | A kind of method for preparing alkene compound from alkyne compound |
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