CN107954814A - The method of phenylacetylene selection hydrogenation in eight fraction of carbon - Google Patents
The method of phenylacetylene selection hydrogenation in eight fraction of carbon Download PDFInfo
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- CN107954814A CN107954814A CN201610898353.7A CN201610898353A CN107954814A CN 107954814 A CN107954814 A CN 107954814A CN 201610898353 A CN201610898353 A CN 201610898353A CN 107954814 A CN107954814 A CN 107954814A
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- catalyst
- phenylacetylene
- fraction
- carbon
- 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 146
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000005336 cracking Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 238000004230 steam cracking Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 7
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 141
- 230000008859 change Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000012545 processing Methods 0.000 description 21
- 229940058172 ethylbenzene Drugs 0.000 description 20
- 239000007868 Raney catalyst Substances 0.000 description 17
- 229910000564 Raney nickel Inorganic materials 0.000 description 17
- 231100000614 poison Toxicity 0.000 description 16
- 239000002574 poison Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- 238000001802 infusion Methods 0.000 description 9
- 238000007689 inspection Methods 0.000 description 8
- 231100000572 poisoning Toxicity 0.000 description 7
- 230000000607 poisoning effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 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
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- NEBFBVFMEJNMTO-UHFFFAOYSA-N acetylene;benzene Chemical group C#C.C1=CC=CC=C1 NEBFBVFMEJNMTO-UHFFFAOYSA-N 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
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 methyl mercaptan Compound Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The present invention relates to a kind of method of phenylacetylene selection hydrogenation in eight fraction of carbon, mainly solve that styrene loss late existing in the prior art is high, the technical problem of stability difference.The present invention, as raw material, is 10~80 DEG C in reaction temperature by using eight cut of cracking carbon and hydrogen using preparing ethylene by steam cracking byproduct in process, and reaction pressure is 0.1~2.0MPa, when green oil volume space velocity is 0.5~2.0 small‑1, hydrogen/oil volume ratio is 5~20：Under conditions of 1, raw material reacts with being contacted containing sulfur catalyst, the phenylacetylene component in raw material is set to change into styrene, and original styrene does not lose in raw material, wherein it is 0.01 5% technical solution by weight percentage containing sulfur content in sulfur catalyst, preferably solves the problems, such as this, in the industrial production available for phenylacetylene selective hydrogenation in cracking eight fraction of carbon.
Description
Technical field
The present invention relates to a kind of method of phenylacetylene selective hydrogenation in eight fraction of carbon, especially with regard to steam cracking second
Cracking eight fraction of carbon of alkene byproduct in process takes off the method for phenylacetylene.
Background technology
Styrene (ST) is the important monomer for producing polystyrene (PS), ABS resin and butadiene-styrene rubber etc..At present, generation
The production method of styrene mainly has ethylbenzene dehydrogenation method, epoxypropane-vinyl benzene (PO/SM) co-production method, drippolene to take out in boundary
Put forward distillation recovery method and butadiene synthetic method etc..Although ethylbenzene dehydrogenation method is to produce the main method of styrene both at home and abroad at present
(its production capacity accounts for the 90% of world's styrene total productive capacity).It is but in recent years, large-scale with ethene scale
Change, especially the numerous and confused of megaton ethylene unit starts so that extracting and reclaiming styrene technology becomes standby from drippolene
One of concerned volume increase styrene technology.
Drippolene is the important by-product of ethylene industry, and yield is approximately the 60%~70% of ethylene production capacity, containing big
About 4%~6% styrene.Traditional processing method is to carry out two-stage hydrogenation, wherein benzene to C6~C8 cuts in drippolene
Ethene is saturated to ethylbenzene, or is together used as gasoline blending component, or the raw material as C8 aromatics isomerizations with dimethylbenzene.Hydrogenation
The ratio of ethylbenzene and dimethylbenzene isomer about 1 in drippolene afterwards：1, high ethyl-benzene level reduces the material as two
The value of toluene device raw material, these ethylbenzene have impact on the disposal ability of para-xylene production unit, add xylene isomerization
Change the internal circulating load in circuit.
For larger ethene enterprise, if first styrene can be separated before pyrolysis gasoline hydrogenation, then
Considerable benefit can be produced, brings considerable economic benefit：1. may separate out purity is more than 99.7% styrene, styrene from
Fuel price is upgraded to chemical values, and recyclable mixed xylenes, for producing the isomers such as paraxylene, dimethylbenzene evaporates
Part is upgraded to chemical values from fuel value.By taking a set of 1,000,000 tons/a ethylene units as an example, it can inexpensively obtain 2.4~
The styrene of 4.2kt/a；2. the hydrogenation load of device can be greatly reduced, hydrogen consumption is reduced；Taken off 3. production cost is ethylbenzene
The 1/2 of hydrogen.
Styrene is recycled from drippolene and uses extractive distillation method.Due to phenylacetylene (PA) and styrene chemical constitution phase
Seemingly, both interactions between extractant are also similar, therefore can not achieve the effective of styrene and PA by extracting rectifying
Separation, it is necessary to first to styrene will be extracted again after phenylacetylene selective hydrogenation and removing.And PA is also styrene copolymerized, block at the same time
The poisonous substance of polymerization, such as increases catalyst consumption amount during anionic polymerization of styrene, influences chain growth and polymerization, also result in poly-
Styrene performance depreciation, such as changes colour, degrades, is spoiled and discharge smell.Therefore, high selectivity phenylacetylene selection hydrogenation is developed
Catalyst and technique become the core of recycling vinyl benzene with pyrolysis gasoline technology.In addition, need it is specifically intended that how to greatest extent
The loss late of reduction styrene be the whether competitive key of recycling vinyl benzene with pyrolysis gasoline.
Disclose and a kind of hydrogenated by means of catalyst containing the benzene second in styrene dielectric in Chinese patent CN1298376A
The method of alkynes, it comes by using nickel content for the Raney nickel being carried on carrier and bubbling bed reactor of 10~25wt%
Hydrogenation is containing the phenylacetylene in styrene dielectric, but the method that the patent only introduces phenylacetylene selection hydrogenation from technology controlling and process, but
Under high stringent process conditions, its Hydrogenation is unsatisfactory, and the secondly loss to styrene during this is not described in detail.
Described in Chinese patent CN1087892A a kind of method for hydrogenation come in purified styrene stream the method for phenylacetylene and
Equipment, it dilutes hydrogen by adding using hydrogen addition diluent such as nitrogen, by hydrogen and the selectivity modification of catalyst
Agent such as carbon monoxide mixes, and discharges gas with ethylbenzene dehydrogenation to provide hydrogen and hydrogenate phenylacetylene contaminant with multistage catalytic reactor
For styrene, but the selective hydration acetylene removal method of low concentration such as 300ppm phenylacetylene contents is only described in the patent, at the same time
(95% or so) low to phenylacetylene hydrogenation rate, and styrene loss late is 0.2% or so.
Chinese patent CN1852877A discloses a kind of method of the hydrogenation of phenylacetylene impurity in the presence of styrene monomer.Will
Styrene monomer stream comprising a small amount of phenylacetylene and hydrogeneous hydrogenated gas supply hydrogenation reactor.Make styrene monomer stream
Contacted with hydrogen with the bed comprising catalyst, the catalyst is included in the copper compound of the reduction on Θ alumina supports.Hydrogen
Change at least 60 DEG C of reaction temperature and at least operated under 30psig pressure, hydrogenation of phenylacetylene generation styrene.Hydrogenated gas is nitrogen
With the mixture of hydrogen, the technology reaction temperature is higher, and phenylacetylene hydrogenation rate is low, about 70%, while there are catalyst life compared with
It is short, and there are the problem of loss late high (about 3% or so) for styrene.
The method that Chinese patent CN101475438A discloses phenylacetylene selection hydrogenation in the presence of a kind of styrene.With carbon containing
Nickel or palladium oxide be catalyst, the hydrocarbon material containing phenylacetylene and hydrogen are contacted with catalyst in the reactor so that
Hydrogenate phenylacetylene is styrene in material, but this method needs to carry out pre- carbon deposit to catalyst at a certain temperature in use
Technique, is unfavorable for practical application.
The content of the invention
The technical problems to be solved by the invention are that styrene loss late existing in the prior art is high, phenylacetylene hydrogenation rate
Technical problem low, stability is poor, there is provided a kind of method of phenylacetylene selection hydrogenation in new cracking eight fraction of carbon.This method and
Have the advantages that styrene loss late is low, stability is good.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of method of phenylacetylene selection hydrogenation in eight fraction of carbon, with the cracking carbon of preparing ethylene by steam cracking byproduct in process
Eight cuts and hydrogen are raw material, contact and react with catalyst, the phenylacetylene component in raw material is changed into styrene, and former
Original styrene does not lose in material, and the catalyst is containing sulfur catalyst, wherein containing sulfur content in sulfur catalyst with catalyst weight
It is 0.01~5% to measure percentages.
In above-mentioned technical proposal, catalyst is handled to obtain sulfur-bearing using organic compounds containing sulfur of the carbon number less than 3
Catalyst.Preferably, above-mentioned processing carries out in hydrogen atmosphere under normal temperature and pressure.
In above-mentioned technical proposal, the carbon number less than 3 organic compounds containing sulfur include dimethyl disulfide, carbon disulfide,
At least one of methyl mercaptan, methyl sulfide.
It is described to further include active component and carrier containing sulfur catalyst in above-mentioned technical proposal, the activearm containing sulfur catalyst
At least one of metallic nickel, copper, palladium are selected from, when preferred metallic nickel is catalyst, its content is with catalyst weight percentage
Than being calculated as 10~40%；When preferred metallic copper is catalyst, its content is calculated as 20~60% with catalyst weight percent；When
It is preferred that when Metal Palladium is catalyst, its content is calculated as 0.1~2% with catalyst weight percent.
In above-mentioned technical proposal, the carrier is included selected from aluminium oxide, at least one of MCM-41 molecular sieves, the oxidation
Aluminium includes gamma-alumina, θ aluminium oxide.
In above-mentioned technical proposal, sulfur content is calculated as 0.05~2% with catalyst weight percent.
In above-mentioned technical proposal, reaction process condition is that reaction temperature is 10~80 DEG C, reaction pressure for 0.1~
2.0MPa, when green oil volume space velocity is 0.5~2.0 small-1, hydrogen/oil volume ratio is 5~20：1.Preferable reaction process condition
It it is 20~50 DEG C for reaction temperature, reaction pressure is 0.2~1.0MPa, when green oil air speed is 1.0~1.5 small-1, hydrogen/oil body
Product is than being 8~15：1.
In above-mentioned technical proposal, crack in eight fraction of carbon, by weight percentage, phenylacetylene content 0.1~3%, benzene second
Alkene content 20~70%.
The preparation method containing sulfur catalyst of the invention is：The solution that carrier is made into the desired amount of active component is impregnated,
Catalyst precarsor is obtained, after hydrogen and nitrogen activation, obtains containing active constituent catalyst, it is at normal temperatures and pressures, organic with sulfur-bearing
Compound carries out catalyst to poison processing.
The hydrogenation reaction of phenylacetylene is a typical consecutive reaction, and intermediate product is styrene, if excessive hydrogenation is generation
Ethylbenzene, and in cracking eight fraction of carbon recycling styrene, the added value of ethylbenzene is well below styrene, while micro benzene
Acetylene exists to the separating of subsequent styrene, refines and decoloration process is unfavorable, for this reason, how maximumlly to convert phenylacetylene, together
When reduce the loss of styrene to greatest extent, be the key for cracking eight fraction of carbon recycling styrene.During phenylacetylene hydrogenation,
Phenylacetylene hydrogenation is that the reaction activity of styrene less than styrene hydrogenation is ethylbenzene, this is from kinetics angle to phenylacetylene
Selection hydrogenation provide important theoretical foundation.Present inventor, which studies, to be found, advance to the nickel after reduction, copper or palladium catalyst
Phenylacetylene hydrogenation processing is carried out again after carrying out sulfur poisoning at normal temperatures and pressures, and catalyst shows more preferable phenylacetylene hydrogenation selection
Property, styrene does not lose in not only feeding, but also a part is hydrogenated to styrene during the reaction in phenylacetylene.Skill of the present invention
In art scheme, sulfur poisoning processing is carried out using preferable Raney nickel, organic sulfur is preferentially adsorbed on the Ni surfaces of little crystal grain, suppresses
The high activity of little crystal grain Ni converts phenylacetylene, it can be achieved that maximizing, while the loss late of styrene minimizes, and catalyst
Stability can be obviously improved.
Optimal technical scheme using the present invention, using aluminium oxide as carrier, nickel be active component catalyst, sulfur content with
Catalyst weight percent is calculated as 0.05~2%, with phenylacetylene content 0.1~3%, the cracking carbon of styrene-content 20~70%
Eight fractions are raw material, are 20~50 DEG C in reaction temperature, and reaction pressure is 0.2~1.0MPa, and green oil air speed is 1.0~1.5
Hour-1, hydrogen/oil volume ratio is 8~15：Under conditions of 1, phenylacetylene hydrogenation conversion ratio reaches as high as 100%, and styrene is up to nothing
Loss even negative growth, catalyst stability is good, achieves preferable technique effect.
Compared with the conventional method, advantages of the present invention：(1) sulphur of catalyst poison treatment process (it is gentle, it is easy to operate,
Beneficial to practical application (2) phenylacetylene hydrogenation high selectivity, styrene loss late is low, stability is good.
Below by embodiment, the present invention is further elaborated.But these embodiments are not anyway to the present invention
Scope be construed as limiting.
Embodiment
【Embodiment 1】
Using gamma-alumina as carrier, use infusion process to prepare load capacity as 14% Raney nickel precursor 15g, use preceding use
After hydrogen and nitrogen are when 420 DEG C of activation 4 of temperature are small, Raney nickel is obtained.At normal temperatures and pressures, with dimethyl disulfide to catalysis
Agent poison processing 2 it is small when, be 0.13% through measuring sulfur content on catalyst, by weight percentage, containing 0.28% benzene second
Alkynes, 40% styrene, eight fraction of cracking carbon of 16% ethylbenzene are raw material, are 38 DEG C, reaction pressure 0.3MPa in reaction temperature,
When green oil air speed is 1.2 small-1, hydrogen/oil volume ratio is 9：Under conditions of 1, make raw material using fixed bed reactors and poison place
The Raney nickel contact of reason, is reacted, reaction result is：Reaction slips out phenylacetylene content 1.0ppm in thing, styrene loss rate
For 0.8%.
【Embodiment 2】
Using gamma-alumina as carrier, use infusion process to prepare load capacity as 37% Raney nickel precursor 15g, use preceding use
After hydrogen and nitrogen are when 420 DEG C of activation 4 of temperature are small, Raney nickel is obtained.Condition processing is poisoned using identical with embodiment 1
3 it is small when, it is 0.84% catalyst to obtain sulfur content, by weight percentage, containing 0.31% phenylacetylene, 28% styrene, 14%
Eight fraction of cracking carbon of ethylbenzene is raw material, is 30 DEG C, reaction pressure 0.5MPa in reaction temperature, green oil air speed is small for 1.4
When-1, hydrogen/oil volume ratio is 11：Under conditions of 1, raw material is set to be contacted with poisoning the Raney nickel of processing using fixed bed reactors,
Reacted, reaction result is：Reaction slips out phenylacetylene inspection in thing and does not measure, and styrene loss rate is 0.5%.
【Embodiment 3】
Using θ+γ mixed phases aluminium oxide as carrier, use infusion process to prepare load capacity as 30% Raney nickel precursor 15g, make
With preceding hydrogen and nitrogen when 420 DEG C of activation 4 of temperature are small after, obtain Raney nickel.Using carbon disulfide and with embodiment 1
It is identical poison condition processing 5 it is small when, it is 1.0% catalyst to obtain sulfur content, by weight percentage, containing 0.24% benzene second
Alkynes, 30% styrene, eight fraction of cracking carbon of 17% ethylbenzene are raw material, are 32 DEG C, reaction pressure 0.4MPa in reaction temperature,
When green oil air speed is 1.1 small-1, hydrogen/oil volume ratio is 10：Under conditions of 1, make raw material using fixed bed reactors and poison place
The Raney nickel contact of reason, is reacted, reaction result is：Reaction slips out phenylacetylene inspection in thing and does not measure, and styrene loss rate is
0.2%.
【Embodiment 4】
Using θ+γ mixed phases aluminium oxide as carrier, use infusion process to prepare load capacity as 24% Raney nickel precursor 15g, make
With preceding hydrogen and nitrogen when 420 DEG C of activation 4 of temperature are small after, obtain Raney nickel.Using methyl sulfide and with 1 phase of embodiment
With poison condition processing 6 it is small when, it is 1.5% catalyst to obtain sulfur content, by weight percentage, containing 1.2% phenylacetylene,
36% styrene, eight fraction of cracking carbon of 20% ethylbenzene are raw material, are 32 DEG C, reaction pressure 0.4MPa in reaction temperature, newly
When fresh oil air speed is 1.1 small-1, hydrogen/oil volume ratio is 14：Under conditions of 1, make raw material using fixed bed reactors and poison processing
Raney nickel contact, reacted, reaction result is：Reaction slips out in thing phenylacetylene inspection and does not measure, styrene loss rate for-
0.4%.
【Embodiment 5】
Using MCM-41 molecular sieves as carrier, use infusion process to prepare load capacity as 27% Raney nickel precursor 15g, use
After preceding use hydrogen and nitrogen are when 420 DEG C of activation 4 of temperature are small, Raney nickel is obtained.Condition is poisoned using identical with embodiment 1
Handle 5 it is small when, it is 1.7% catalyst to obtain sulfur content, by weight percentage, containing 0.72% phenylacetylene, 34% styrene,
Eight fraction of cracking carbon of 18% ethylbenzene is raw material, is 36 DEG C, reaction pressure 0.3MPa in reaction temperature, green oil air speed is
1.2 it is small when-1, hydrogen/oil volume ratio is 12：Under conditions of 1, make raw material using fixed bed reactors and poison the Raney nickel of processing
Contact, is reacted, reaction result is：Reaction slips out phenylacetylene inspection in thing and does not measure, and styrene loss rate is 0.
【Embodiment 6】
Using θ+γ mixed phases aluminium oxide as carrier, use infusion process to prepare load capacity as 36% copper catalyst precursors 15g, make
With preceding hydrogen and nitrogen when 280 DEG C of activation 4 of temperature are small after, obtain copper catalyst.Using the mixed of carbon disulfide and methyl mercaptan
Compound and it is identical with embodiment 1 poison condition processing 2 it is small when, it is 0.9% catalyst to obtain sulfur content, with percentage by weight
Meter, eight fraction of cracking carbon containing 0.31% phenylacetylene, 18% styrene, 10% ethylbenzene is raw material, is 44 DEG C in reaction temperature, instead
It is 0.5MPa to answer pressure, when green oil air speed is 1.0 small-1, hydrogen/oil volume ratio is 14：Under conditions of 1, using fixed bed reaction
Device makes raw material be contacted with poisoning the copper catalyst of processing, is reacted, and reaction result is：Reaction slips out phenylacetylene 3ppm in thing,
Styrene loss rate is 0.
【Embodiment 7】
Using θ+γ mixed phases aluminium oxide as carrier, use infusion process to prepare load capacity as 20% copper catalyst precursors 15g, make
With preceding hydrogen and nitrogen when 280 DEG C of activation 4 of temperature are small after, obtain copper catalyst.Using methyl mercaptan and with 1 phase of embodiment
With poison condition processing 3 it is small when, it is 0.6% catalyst to obtain sulfur content, by weight percentage, containing 0.29% phenylacetylene,
20% styrene, eight fraction of cracking carbon of 17% ethylbenzene are raw material, are 48 DEG C, reaction pressure 0.4MPa in reaction temperature, newly
When fresh oil air speed is 1.1 small-1, hydrogen/oil volume ratio is 14：Under conditions of 1, make raw material using fixed bed reactors and poison processing
Copper catalyst contact, reacted, reaction result is：Reaction slips out phenylacetylene 9ppm in thing, and styrene loss rate is 0.
【Embodiment 8】
Using θ+γ mixed phases aluminium oxide as carrier, infusion process is used to prepare load capacity as 0.5% palladium catalyst precursor 15g,
Using it is preceding with hydrogen and nitrogen when 300 DEG C of activation 4 of temperature are small after, obtain palladium catalyst.Poisoned using identical with embodiment 1
When condition processing 1 is small, it is 0.1% catalyst to obtain sulfur content, by weight percentage, containing 1.8% phenylacetylene, 55% benzene second
Alkene, eight fraction of cracking carbon of 20% ethylbenzene are raw material, are 30 DEG C, reaction pressure 0.3MPa in reaction temperature, green oil air speed
For 1.0 it is small when-1, hydrogen/oil volume ratio is 12：Under conditions of 1, make raw material using fixed bed reactors and poison the palladium chtalyst of processing
Agent contacts, and is reacted, reaction result is：Reaction slips out phenylacetylene inspection in thing and does not measure, and styrene loss rate is 0.6%.
【Embodiment 9】
Using θ+γ mixed phases aluminium oxide as carrier, infusion process is used to prepare load capacity as 2.0% palladium catalyst precursor 15g,
Using it is preceding with hydrogen and nitrogen when 300 DEG C of activation 4 of temperature are small after, obtain palladium catalyst.Using carbon disulfide and with implementation
Example 1 it is identical poison condition processing 2 it is small when, it is 0.3% catalyst to obtain sulfur content, by weight percentage, containing 2.5% benzene second
Alkynes, 60% styrene, eight fraction of cracking carbon of 14% ethylbenzene are raw material, are 28 DEG C, reaction pressure 0.3MPa in reaction temperature,
When green oil air speed is 1.0 small-1, hydrogen/oil volume ratio is 14：Under conditions of 1, make raw material using fixed bed reactors and poison place
The palladium catalyst contact of reason, is reacted, reaction result is：Reaction slips out phenylacetylene inspection in thing and does not measure, and styrene loss rate is
1.0%.
【Comparative example 1】
It is that catalyst does not carry out poisoning processing, other conditions and raw material according to each step and condition of embodiment 4
All same, reaction result are：Reaction slips out phenylacetylene inspection in thing and does not measure, and styrene loss rate is 0.3%.
【Comparative example 2】
It is that catalyst does not carry out poisoning processing, other conditions and raw material according to each step and condition of embodiment 7
All same, reaction result are：Reaction slips out phenylacetylene 4ppm in thing, and styrene loss rate is 0.8%.
【Comparative example 3】
It is that catalyst does not carry out poisoning processing, other conditions and raw material according to each step and condition of embodiment 8
All same, reaction result are：Reaction slips out phenylacetylene inspection in thing and does not measure, and styrene loss rate is 5.0%.
Claims (10)
1. a kind of method of phenylacetylene selection hydrogenation in eight fraction of carbon, with the cracking carbon eight of preparing ethylene by steam cracking byproduct in process
Fraction and hydrogen are raw material, contact and react with catalyst, the phenylacetylene component in eight fraction of material carbon is changed into benzene second
Alkene, it is characterised in that the catalyst is containing sulfur catalyst, is calculated as containing sulfur content in sulfur catalyst with catalyst weight percent
0.01~5%.
2. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that small with carbon number
Organic compounds containing sulfur in 3 obtains containing sulfur catalyst to the catalyst progress adsorption treatment after activation.
3. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that described low point
The sulfur-containing compound of son amount includes at least one of dimethyl disulfide, carbon disulfide, methyl mercaptan, methyl sulfide.
4. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that the sulfur-bearing
Catalyst further includes active component and carrier, and the active component containing sulfur catalyst is at least one in metallic nickel, copper, palladium
Kind.
5. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that sulfur content with
Catalyst weight percent is calculated as 0.05~2%.
6. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that catalyst is lived
Property component is nickel, its content is calculated as 10~40% with catalyst weight percent.
7. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that catalyst is lived
Property component is copper, its content is calculated as 20~60% with catalyst weight percent.
8. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that catalyst is lived
Property component is palladium, its content is calculated as 0.1~2% with catalyst weight percent.
9. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that reaction temperature
For 10~80 DEG C, reaction pressure is 0.1~2.0MPa, when green oil volume space velocity is 0.5~2.0 small-1, hydrogen/oil volume ratio is 5
~20：1.
10. the method for phenylacetylene selective hydrogenation in eight fraction of carbon according to claim 1, it is characterised in that cracking carbon eight
In fraction, by weight percentage, phenylacetylene content 0.1~3%, styrene-content 20~70%.
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| CN114181032A (en) * | 2020-09-15 | 2022-03-15 | 中国石油天然气股份有限公司 | Method for removing phenylacetylene by selective hydrogenation of carbon eight fraction |
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