CN110639607B - Catalyst for directly preparing styrene by catalyzing acetylene and preparation method and application thereof - Google Patents
Catalyst for directly preparing styrene by catalyzing acetylene and preparation method and application thereof Download PDFInfo
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- CN110639607B CN110639607B CN201910899024.8A CN201910899024A CN110639607B CN 110639607 B CN110639607 B CN 110639607B CN 201910899024 A CN201910899024 A CN 201910899024A CN 110639607 B CN110639607 B CN 110639607B
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- acetylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002808 molecular sieve Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003245 coal Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 239000010955 niobium Substances 0.000 claims abstract description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 17
- 239000012702 metal oxide precursor Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 12
- 238000001994 activation Methods 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007725 thermal activation Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 26
- 239000000376 reactant Substances 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- -1 metal oxide modified molecular sieve Chemical class 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NEBFBVFMEJNMTO-UHFFFAOYSA-N acetylene;benzene Chemical group C#C.C1=CC=CC=C1 NEBFBVFMEJNMTO-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of catalysts, and particularly discloses a catalyst for directly preparing styrene by catalyzing acetylene, and a preparation method and application thereof. The catalyst is a metal and metal oxide modified molecular sieve, metal (niobium, molybdenum, tungsten and zirconium) oxide components for modifying acid sites and metal (palladium, platinum and ruthenium) components for adsorbing and activating reactant molecules are impregnated step by step and limited in pore channels of the molecular sieve by adopting a step impregnation method, the catalytic effect is changed by regulating the number of B acid and L acid in the molecular sieve through metal oxides, and meanwhile, highly dispersed metal site activated reactant molecules are introduced, intermediate species are stabilized, and the performance of the catalyst is improved. The invention breaks through the traditional styrene technical route, widens the downstream products of coal-based acetylene, synthesizes the styrene by directly reacting the acetylene and the benzene under the action of the catalyst, has mild reaction conditions, and has short technical route, low energy consumption and obvious technical advantages compared with the traditional styrene technical route.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for directly preparing styrene by catalyzing acetylene and a preparation method and application thereof.
Background
Styrene is used as an important chemical basic raw material and is mainly used for synthesizing rubber and resin, downstream products of the styrene are mainly products such as styrene butadiene rubber, polystyrene resin, ABS engineering plastics and the like, and the industrial application is wide and the demand is high. At present, styrene is basically from petrochemical technology, wherein nearly 90% of capacity is mainly produced by ethylbenzene dehydrogenation technology, a process route is firstly to prepare ethylbenzene by benzene and ethylene, and then styrene is prepared by ethylbenzene dehydrogenation, the process route is long, the dehydrogenation process is generally a negative pressure adiabatic reaction, the reaction temperature is as high as 600-630 ℃, the process water consumption is large, the energy consumption is high, and the current research is mainly focused on the development of a low-temperature low-water-ratio dehydrogenation catalyst.
In the coal chemical industry, the technology for preparing acetylene by using coal as a raw material through a calcium carbide process is mature. At present, the yield of polyvinyl chloride (PVC) which is the main downstream product of acetylene is excessive seriously, the industrial profit is low, and the industrial chain of the downstream product of acetylene is urgently needed to be expanded.
Aiming at the energy structure characteristics of lean oil and rich coal in China, the development of a high-efficiency clean coal resource technology for replacing petrochemical industry is necessary.
If the coal-based acetylene can be utilized and the coal-based acetylene route is directly converted to prepare the styrene, the technology has the advantages of shorter process route and higher technical cost, and has wide application prospect. However, no relevant research and report is found at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a catalyst for catalyzing acetylene to directly prepare styrene, and a preparation method and application thereof.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
in a first aspect, the invention provides a catalyst for catalyzing acetylene to directly prepare styrene and a preparation method thereof.
The catalyst is a molecular sieve modified by metal and metal oxide; the catalyst comprises a B acid position and an L acid-base position, wherein the B acid is proton hydrogen, the L acid is non-framework aluminum or metal cations for balancing charges, and oxygen adjacent to the L acid position is used as the L base position.
Activating acetylene molecules to C by utilizing B acid sites on the surface of the catalyst+Reacting intermediate species, activating and adsorbing benzene ring by L acid on the surface of the catalyst, activating C-H bond of benzene by oxygen at adjacent L alkali position to form C-reaction intermediate species of benzene, and performing C-reaction+Species and C-Species coupling forms new C-C bonds and corresponding styrene products. Namely a catalyst with the active structure of the synergistic action of B acid and L acid-alkali pair.
Because B acid on the surface of the molecular sieve belongs to strong acid, the acid catalysis effect is obvious, the acetylene activation process is easy to further deepen to cause side reactions such as acetylene cracking, polymerization and the like, the catalyst is easy to be deactivated by carbon deposition, the self L acid effect of the molecular sieve is weak, the adsorption and activation effects on benzene are not strong, and the activation adsorption on benzene reaction species needs to be improved to improve the generation of a target product, namely styrene.
The invention researches and discovers that the proper metal and metal oxide dosage can effectively adjust the B acid and L acid quantity of the catalyst and enhance the activated adsorption and stabilization effects of the catalyst on reactant molecules and intermediate species.
Therefore, by introducing L acid oxides such as niobium, molybdenum, tungsten, zirconium and the like into the molecular sieve, on one hand, B acid sites on the surface of a part of the molecular sieve can be shielded so as to reduce the B acid amount and inhibit side reactions, on the other hand, the L acid amount can be increased, the activated adsorption of a reactant benzene is improved, and the catalyst performance is improved.
Meanwhile, on the basis, precious metals such as palladium, platinum and ruthenium are added to enhance the chemical adsorption effect on reaction species, enhance the chemical adsorption and activation of the catalyst on benzene and acetylene and the stability of important intermediate species, further promote the reaction behavior of the catalyst on the preparation of styrene from acetylene, and enhance the catalytic activity and the yield of styrene.
Therefore, in the metal and metal oxide modified molecular sieve of the present invention, the metal is any one of palladium, platinum and ruthenium, and the metal oxide is an oxide of any one of niobium, molybdenum, tungsten and zirconium.
In the catalyst, the mass ratio of metals (palladium, platinum and ruthenium), metals (niobium, molybdenum, tungsten and zirconium) in metal oxides and molecular sieves is (0.5-5): (5-8): 91-94).
Further, the molecular sieve is an H-ZSM-5 molecular sieve, and the silica-alumina ratio (the molar ratio of silicon atoms to aluminum atoms in the molecular sieve, i.e. the mole ratio of silicon to aluminum) of the molecular sieve is 200 to 300, for example, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, preferably 260.
Further, the preparation method of the catalyst specifically comprises the following steps:
(1) carrying out roasting thermal activation treatment on the molecular sieve;
(2) adding a metal oxide precursor into deionized water to prepare a metal oxide precursor solution, impregnating the molecular sieve subjected to thermal activation treatment by using the metal oxide precursor solution, and performing ultrasonic treatment in the impregnation process; drying and roasting the catalyst precursor after ultrasonic treatment to obtain a catalyst precursor;
(3) adding a metal precursor into dilute nitric acid to prepare a metal precursor solution, impregnating the catalyst precursor obtained in the step (2) by using the metal precursor solution, and carrying out ultrasonic treatment in the impregnation process; and drying and roasting the catalyst after ultrasonic treatment to obtain a catalyst sample.
And granulating and screening the finished catalyst product by 40-60 meshes to obtain the catalyst product for directly preparing styrene by catalyzing acetylene.
In the step (1), the roasting heat activation treatment temperature of the molecular sieve is 550-600 ℃, and the roasting time is 6-8 hours. The heat activation treatment of the molecular sieve can remove physically adsorbed water on one hand, and on the other hand, partial non-framework aluminum is generated due to the condensation of hydroxyl on the surface of the molecular sieve in the high-temperature treatment process to form an L acid center.
In the step (2), the metal oxide precursor is any one of niobium nitrate, niobium oxalate, niobium chloride, ammonium molybdate, molybdenum nitrate, molybdenum sulfate, molybdenum chloride, ammonium tungstate, tungsten chloride, zirconium nitrate, zirconium chloride and zirconium sulfate; any one of niobium oxalate, ammonium molybdate, ammonium tungstate and zirconium nitrate is preferred;
in the step (3), the metal precursor is a nitrate of any one of palladium, platinum and ruthenium.
Furthermore, the power of the ultrasonic treatment is preferably 70-100W, such as 80W, the time is preferably 2-3 hours, and the ultrasonic treatment is favorable for uniformly dispersing the impregnation liquid in the molecular sieve pore channel.
Preferably, in the roasting process related to the step (2) and the step (3), the roasting temperature is controlled to be 350-400 ℃, the roasting time is 4-5 hours, and the surface of the molecular sieve can be better modified.
In the second aspect, in order to break through the technical route of the traditional styrene process, widen the downstream products of coal-based acetylene and remove the productivity, the invention further provides the application of the catalyst in the process of directly preparing styrene from acetylene (especially coal-based acetylene), and develops a technology for preparing styrene from coal-based acetylene.
Wherein the reaction conditions of the reduction treatment performed on the catalyst are as follows: hydrogen/nitrogen is 1:2 to 1:5, preferably 1: 3; the reduction space velocity is 800-1500 h-1Preferably 1000h-1(ii) a The reduction temperature is 300-350 ℃, and the reduction time is 1-2 hours.
In the catalytic reaction, the molar ratio of benzene to acetylene (benzyne ratio) is 1: 1-5: 1, preferably 3: 1; the reaction temperature is 250-300 ℃, and preferably 280 ℃; the airspeed is 5000 ~ 10000h-1Preferably 8000h-1(ii) a The reaction pressure is 0-0.8 MPa, preferably 0.5 MPa.
Further objective experimental research shows that benzene and acetylene with a benzene-acetylene ratio of about 3:1 are adopted, and the catalyst is catalyzed at the temperature of about 280 ℃ and the space velocity of 8000h -1The reaction is carried out under the conditions of about 0.5MPa of reaction pressure to synthesize the styrene, and higher acetylene conversion rate, styrene yield and styrene selectivity can be obtained.
The raw materials or reagents involved in the invention are all common commercial products, and the operations involved are all routine operations in the field unless otherwise specified.
The preferred conditions described above may be combined with each other to arrive at a specific embodiment, based on general knowledge in the art.
The invention has the beneficial effects that:
the invention provides a catalyst capable of catalyzing acetylene to directly prepare styrene, which is characterized in that a step-by-step impregnation method is adopted, a metal oxide component for modifying an acid site and a metal component for adsorbing and activating reactant molecules are impregnated step by step and limited in a pore channel of a molecular sieve, the number of B acid and L acid in the molecular sieve is adjusted by the metal oxide to change the catalytic effect, and meanwhile, highly dispersed metal site activated reactant molecules are introduced to stabilize intermediate species and improve the performance of the catalyst. The preparation method of the catalyst is simple to operate, good in repeatability and convenient for industrial application.
Based on the characteristics and functions of the catalyst, the invention further develops a technology for preparing styrene from coal-based acetylene, breaks through the traditional technical route of styrene technology, widens the downstream products of coal-based acetylene and removes the productivity, and synthesizes styrene by directly reacting acetylene and benzene under the action of the catalyst.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
(1) Catalyst preparation
Catalyst component palladium: niobium: the mass ratio of the H-ZSM-5 molecular sieve is 0.5:5: 94.5. Selecting an H-ZSM-5 molecular sieve with the silica-alumina ratio of 260, and carrying out heat activation roasting treatment at the roasting temperature of 550 ℃ for 8 hours; then weighing 2.89g of niobium oxalate and 9.45g of activated molecular sieve according to the measurement; adding niobium oxalate into 10mL of deionized water, heating and stirring to form uniform metal oxide precursor solution; dropwise adding the metal oxide precursor solution into a molecular sieve for dipping, and carrying out ultrasonic treatment for 2 hours after dropwise adding; drying the mixture after ultrasonic treatment at the drying temperature of 80 ℃ for 10 hours; and drying and roasting at 350 ℃ for 5 hours to obtain the catalyst precursor. Weighing 0.11g of palladium nitrate according to the measurement, adding the palladium nitrate into 10mL of dilute nitric acid solution with the concentration of 0.1mol/L, heating and stirring to form uniform metal precursor solution, dropwise adding the metal precursor solution into a catalyst precursor for dipping, and carrying out ultrasonic treatment for 2 hours after the dropwise addition is finished; drying the mixture after ultrasonic treatment at the drying temperature of 80 ℃ for 10 hours; and drying, roasting at 350 ℃ for 5 hours to obtain a catalyst sample, granulating, and screening by 40-60 meshes for later use.
(2) Catalyst evaluation
A fixed bed micro-reaction device is adopted, 5g of catalyst is filled, the dilution volume of quartz sand is 1:1, and the reduction conditions of the catalyst are as follows: hydrogen/nitrogen is 1:3, and the reduction space velocity is 1000h-1The reduction temperature was 300 ℃ and the reduction time was 1 hour. The reaction conditions are as follows: (ii) a phenylalkyne ratio of 3: 1; the reaction temperature is 280 ℃; the space velocity is 5000h-1(ii) a The reaction pressure was 0.5 MPa. The evaluation results are shown in Table 1 below.
Example 2
(1) Catalyst preparation
Catalyst component palladium: niobium: the mass ratio of the H-ZSM-5 molecular sieve is 1:8: 91. Selecting an H-ZSM-5 molecular sieve with the silica-alumina ratio of 260, and carrying out heat activation roasting treatment at the roasting temperature of 600 ℃ for 6 hours; then weighing 4.62g of niobium oxalate and 9.1g of activated molecular sieve according to the measurement; adding niobium oxalate into 10mL of deionized water, heating and stirring to form uniform metal oxide precursor solution; dropwise adding the metal oxide precursor solution into a molecular sieve for dipping, and carrying out ultrasonic treatment for 3 hours after dropwise adding; drying after ultrasonic treatment at 100 ℃ for 8 hours; after drying, roasting is carried out, wherein the roasting temperature is 400 ℃, and the roasting time is 4 hours, so as to obtain the catalyst precursor. Weighing 0.22g of palladium nitrate according to the measurement, adding the palladium nitrate into 10mL of dilute nitric acid solution with the concentration of 0.1mol/L, heating and stirring to form uniform metal precursor solution, dropwise adding the metal precursor solution into a catalyst precursor for dipping, and carrying out ultrasonic treatment for 3 hours after the dropwise addition is finished; drying after ultrasonic treatment at 100 ℃ for 8 hours; and drying, roasting at 350 ℃ for 4 hours to obtain a catalyst sample, granulating, and screening by 40-60 meshes for later use.
(2) Catalyst evaluation
The catalyst was evaluated under the same conditions as in example 1, wherein the reduction time was 2 hours, and the evaluation results are shown in Table 1 below.
Example 3
(1) Catalyst preparation
Catalyst component palladium: niobium: the mass ratio of the H-ZSM-5 molecular sieve is 0.8:7: 92.2. Selecting an H-ZSM-5 molecular sieve with the silica-alumina ratio of 260, and carrying out heat activation roasting treatment at the roasting temperature of 550 ℃ for 8 hours; then weighing 4.05g of niobium oxalate and 9.22g of activated molecular sieve according to the measurement; adding niobium oxalate into 10mL of deionized water, heating and stirring to form uniform metal oxide precursor solution; dropwise adding the metal oxide precursor solution into a molecular sieve for dipping, and carrying out ultrasonic treatment for 3 hours after dropwise adding; drying after ultrasonic treatment at 100 ℃ for 8 hours; after drying, roasting is carried out, wherein the roasting temperature is 400 ℃, and the roasting time is 4 hours, so as to obtain the catalyst precursor. Weighing 0.18g of palladium nitrate according to the measurement, adding the palladium nitrate into 10mL of dilute nitric acid solution with the concentration of 0.1mol/L, heating and stirring to form uniform metal precursor solution, dropwise adding the metal precursor solution into a catalyst precursor for dipping, and carrying out ultrasonic treatment for 3 hours after the dropwise addition is finished; drying after ultrasonic treatment at 100 ℃ for 8 hours; and drying, roasting at 350 ℃ for 4 hours to obtain a catalyst sample, granulating, and screening by 40-60 meshes for later use.
(2) The catalyst was evaluated under the same conditions as in example 2, and the evaluation results are shown in Table 1 below.
Example 4
(1) Catalyst preparation was carried out under the same conditions as in example 3 except that 4.05g of niobium oxalate was replaced with 1.43g of ammonium molybdate; that is, molybdenum is used as the metal oxide in this embodiment.
(2) The catalyst was evaluated under the same conditions as in example 2, and the evaluation results are shown in Table 1 below.
Example 5
(1) Catalyst preparation was carried out under the same conditions as in example 3 except that 4.05g of niobium oxalate was replaced with 0.97g of ammonium tungstate; that is, tungsten is used as the metal oxide in this embodiment.
(2) The catalyst was evaluated under the same conditions as in example 2, and the evaluation results are shown in Table 1 below.
Example 6
(1) Catalyst preparation was carried out under the same conditions as in example 3 except that 4.05g of niobium oxalate was replaced with 3.29g of zirconium nitrate; namely, zirconium is used as the metal oxide in this embodiment.
(2) The catalyst was evaluated under the same conditions as in example 2, and the evaluation results are shown in Table 1 below.
Example 7
(1) Catalyst preparation was carried out under the same conditions as in example 3 except that 0.18g of palladium nitrate was replaced with 0.13g of platinum nitrate; namely, platinum is used as the metal in this embodiment.
(2) The catalyst was evaluated under the same conditions as in example 2, wherein the reduction temperature was 350 ℃ and the evaluation results are shown in Table 1 below.
Example 8
(1) Catalyst preparation was carried out under the same conditions as in example 3 except that 0.18g of palladium nitrate was replaced with 0.25g of ruthenium nitrate; namely, ruthenium is used as the metal in this embodiment.
(2) The catalyst was evaluated under the same conditions as in example 2, wherein the reduction temperature was 350 ℃ and the evaluation results are shown in Table 1 below.
TABLE 1 catalyst performance for the preparation of styrene from coal-based acetylene
The results of the above embodiments show that the catalyst can well realize direct preparation of styrene from coal-based acetylene, and the invention well realizes shielding of part of the B acid sites on the surface of the molecular sieve by introducing L acid oxides such as niobium, molybdenum, tungsten and the like into the molecular sieve, thereby reducing the B acid amount, inhibiting side reactions, increasing the L acid amount, improving the activated adsorption of the reactant benzene and improving the catalyst performance. Meanwhile, on the basis, precious metals such as palladium, platinum and ruthenium are added to enhance the chemical adsorption effect on reaction species, enhance the chemical adsorption and activation of the catalyst on benzene and acetylene and stabilize important intermediate species, further improve the reaction behavior of the catalyst on preparing styrene from acetylene, and enhance the catalytic activity and the styrene yield.
As seen from the results, comparative examples 1 to 3 found that the metal component in the catalyst: metal oxides by metal: the molecular sieve has better catalytic effect and higher styrene yield when the mass ratio of the molecular sieve is 0.8:7: 92.2; comparative examples 3-6 show that the niobium has slightly higher catalytic effect than molybdenum, tungsten and zirconium; comparative examples 3, 7 and 8 found that ruthenium was superior in catalytic effect to platinum and palladium.
Although the invention has been described in detail with respect to the general description and the specific embodiments thereof, it will be apparent to those skilled in the art that modifications and improvements can be made based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (15)
1. A method for directly preparing styrene from acetylene is characterized in that a molecular sieve modified by metal and metal oxide is used as a catalyst, the catalyst is subjected to reduction treatment, coal-based acetylene and benzene are introduced, and the styrene is synthesized through direct catalytic reaction;
the metal is any one of palladium, platinum and ruthenium, and the metal oxide is any one of niobium, molybdenum, tungsten and zirconium;
in the catalyst, the mass ratio of metal to molecular sieve in metal, metal oxide is 0.5-5: 5-8: 91-94;
the molecular sieve is an H-ZSM-5 molecular sieve, and the silica-alumina ratio is 200-300.
2. The method of claim 1, wherein the silicon to aluminum ratio is 260.
3. The method of claim 1, wherein the catalyst is prepared by a method comprising the steps of:
(1) Carrying out roasting thermal activation treatment on the molecular sieve;
(2) adding a metal oxide precursor into deionized water to prepare a metal oxide precursor solution, impregnating the molecular sieve subjected to thermal activation treatment by using the metal oxide precursor solution, and performing ultrasonic treatment in the impregnation process; drying and roasting the catalyst after ultrasonic treatment to obtain a catalyst precursor;
(3) adding a metal precursor into dilute nitric acid to prepare a metal precursor solution, impregnating the catalyst precursor obtained in the step (2) by using the metal precursor solution, and carrying out ultrasonic treatment in the impregnation process; and drying and roasting the catalyst after ultrasonic treatment to obtain a catalyst sample.
4. The method according to claim 3, wherein in the step (1), the roasting heat activation treatment temperature of the molecular sieve is 550-600 ℃, and the roasting time is 6-8 hours.
5. The method according to claim 3, wherein in the step (2), the metal oxide precursor is any one of niobium nitrate, niobium oxalate, niobium chloride, ammonium molybdate, molybdenum nitrate, molybdenum sulfate, molybdenum chloride, ammonium tungstate, tungsten chloride, zirconium nitrate, zirconium chloride, and zirconium sulfate;
and/or in the step (3), the metal precursor is nitrate of any one of palladium, platinum and ruthenium.
6. The method according to claim 5, wherein in the step (2), the power of the ultrasonic treatment is 70-100W, and the time is 2-3 hours.
7. The method according to claim 5, wherein in the step (2) and the step (3), the roasting temperature is 350-400 ℃ and the roasting time is 4-5 hours.
8. The method according to claim 1, wherein the reaction conditions of the reduction treatment are: hydrogen/nitrogen is 1: 2-1: 5, and the reduction space velocity is 800-1500 h-1The reduction temperature is 300-350 ℃, and the reduction time is 1-2 hours.
9. The method of claim 8, wherein hydrogen/nitrogen is 1: 3.
10. The process as claimed in claim 8, wherein the reduction space velocity is 1000h-1。
11. The method of claim 1, wherein the reaction conditions of the catalytic reaction are the same as the reaction conditions of the catalytic reactionComprises the following steps: the molar ratio of benzene to coal-based acetylene is 1: 1-5: 1, the reaction temperature is 250-300 ℃, and the space velocity is 5000-10000 h-1And the reaction pressure is 0-0.8 MPa.
12. The method of claim 11, wherein the molar ratio of benzene to coal-based acetylene is 3: 1.
13. The process of claim 11, wherein the reaction temperature is 280 ℃.
14. The process according to claim 11, characterized in that the space velocity is 8000h-1。
15. The process of claim 11, wherein the reaction pressure is 0.5 MPa.
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