CN106944139A - A kind of heteropoly acid ammonium salt catalyst and preparation method thereof - Google Patents
A kind of heteropoly acid ammonium salt catalyst and preparation method thereof Download PDFInfo
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- CN106944139A CN106944139A CN201610003172.3A CN201610003172A CN106944139A CN 106944139 A CN106944139 A CN 106944139A CN 201610003172 A CN201610003172 A CN 201610003172A CN 106944139 A CN106944139 A CN 106944139A
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- catalyst
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- silica
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- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005977 Ethylene Substances 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 235000015165 citric acid Nutrition 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004939 coking Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 cracks obtained Chemical compound 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 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 description 3
- 238000005507 spraying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of heteropoly acid ammonium salt catalyst and preparation method thereof.The catalyst includes active component, auxiliary agent and carrier, and active component is ammonium heteropoly acidses, and auxiliary agent is nickel oxide and di-iron trioxide, and carrier is the silica that amorphous silica-alumina is coated.While catalyst of the present invention has higher low temperature active, selectivity and coking resistivity, the stability of catalyst is improved.It is ethylene reaction produced that catalyst of the present invention is particularly suitable for use in the dehydration that the low-concentration ethanol aqueous solution is raw material.
Description
Technical field
It is more particularly to a kind of for carried heteropoly acid ammonium salt in catalysis agent of producing ethylene by ethanol dehydration and preparation method thereof the present invention relates to a kind of heteropoly acid ammonium salt catalyst and preparation method thereof.
Background technology
Ethene is prepared as basic Organic Chemicals and the flagship product of petro chemical industry, about 75% chemical products by raw material of ethene, therefore the size of ethylene yield has become the important symbol for weighing a national oil development of chemical industry level.Traditional ethene mainly cracks obtained, heavy dependence petroleum resources by light petroleum fraction.Day with international energy situation is becoming tight, and petroleum resources are increasingly exhausted, and the new renewable alternative energy source of exploitation has been the task of top priority.
Recently, ethanol particularly recyclable organism preparing ethylene by dehydrating ethanol is increasingly valued by people, and it has green, sustainable, reaction condition gentle and many advantages such as product ethylene purity height.Bio-ethanol is mainly derived from the fermentation of agricultural byproducts, can avoid the dependence to petroleum resources, and this method production ethene is continued to use always in the deficient country of some petroleum resources such as Brazil, India, Pakistan, and this point more has realistic meaning to the country of oil-poor and few oil.Preparing ethylene by dehydrating ethanol, which has, partly or entirely replaces the great potential that ethene is obtained from oil.Therefore, research producing ethylene from dehydration of ethanol has great economic worth and strategic importance.
Catalyst for ethanol delydration to ethylene report is a lot, mainly activated alumina, molecular sieve and heteropoly acid etc..Activated alumina is cheap as catalyst, and activity and selectivity is preferable, but reaction temperature is high, and reaction velocity is low, and high energy consumption, utilization rate of equipment and installations is low.The catalytic activity and selectivity of molecular sieve are high, stable；Reaction temperature is low, and reaction velocity is big, but catalyst life is short, and multiplication factor is small, limits its industrialized production.Heteropoly acid is, with oxygen-containing polyacid of certain structure by oxygen atom ligand bridging, to have the advantages that highly acid by central atom and coordination atom.In producing ethylene from dehydration of ethanol reaction, heteropolyacid catalyst has reaction temperature low, and selectivity is high and the characteristics of high income.
CN201310509561.X discloses the ZSM-5 molecular sieve catalyst that a kind of heteropoly acid is modified, for Ethanol Dehydration ethylene reaction.Catalyst shows higher catalytic activity and selectivity, but be due to carrier ratio surface and aperture it is relatively small, it is impossible to load more heteropoly acids, excessive heteropoly acid can block the duct of carrier, cause catalyst activity reduction, therefore which limit the further raising of catalyst activity.
[Chemical Engineering Technology and the exploitation, 2010,5 (39) such as Li Benxiang：7-9] article that entitled MCM-41 loads Catalyzed by Silicotungstic Acid producing ethylene from dehydration of ethanol is reported, catalyst is prepared using infusion process.CN200910057539.X discloses a kind of catalyst of producing ethylene from dehydration of ethanol.The catalyst is using aluminum oxide as carrier, and active component is heteropoly acid, is prepared using kneading method.Above-mentioned catalyst shows higher catalytic activity and selectivity when using high concentration ethanol as raw material, but when using low-concentration ethanol as raw material, catalyst activity is decreased obviously, and stability is bad.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of heteropoly acid ammonium salt catalyst and preparation method thereof.The catalyst not only has the characteristics of low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and good stability.
Heteropoly acid ammonium salt catalyst of the present invention, including active component, auxiliary agent and carrier, active component are shown in formula for ammonium heteropoly acidses（1）, auxiliary agent is nickel oxide and di-iron trioxide, and carrier is the silica that amorphous silica-alumina is coated；The weight of amorphous silica-alumina accounts for the 15% ~ 45% of vehicle weight, preferably 16% ~ 40%；On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 8% ~ 30%, preferably 12% ~ 25%, and auxiliary agent is in terms of oxide, the content of nickel oxide is 3% ~ 18%, preferably 5% ~ 15%, and the content of di-iron trioxide is 1% ~ 10%, preferably 2% ~ 7%, the content of carrier is 42% ~ 88%, preferably 53% ~ 81%；
Hm(NH4)nYX12O40（1）
Wherein X represents W or Mo, Y represent Si or P；When Y represents Si, m+n=4, n values are 0.1 ~ 1.0；When Y represents P, m+n=3, n values are 0.1 ~ 1.0.
In described heteropoly acid ammonium salt catalyst, ammonium heteropoly acidses are distributed in the outer surface of carrier.
The preparation method of described heteropoly acid ammonium salt catalyst, including：
（1）Prepare the carrier that amorphous silica-alumina coats silica；
（2）Auxiliary agent nickel and iron are loaded into step（1）On the carrier of preparation, catalyst precarsor A is obtained；
（3）Catalyst precarsor A is added in autoclave, reduction treatment is carried out to it using hydrogen；
（4）Polyalcohol and/or furfuryl aldehyde solution are driven into autoclave, Hydrogen Vapor Pressure is then adjusted to 2~4MPa, 0.5~5.0h is reacted at 100~300 DEG C；
（5）By step（4）In reacted catalyst precarsor A filter out, be dried at room temperature, until sample surfaces are without liquid phase, obtain catalyst precarsor B；
（6）By step（5）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated, and obtains catalyst precarsor C；
（7）By step（6）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, through filtering, is dried at 40 DEG C ~ 90 DEG C；Or by step（6）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（8）The aqueous solution of heteropoly acid is added to step（7）In obtained catalyst precarsor D, heating stirring to solution is evaporated, then through drying and being calcined, produces catalyst.
Step（1）In, the carrier of described amorphous silica-alumina cladding silica can be prepared by conventional method.It is preferred to use following method in the present invention to prepare：Silica support is first prepared, is then formed again with amorphous silica-alumina cladding.Wherein silica support can be obtained by silica rubber powder through shaping, dry and roasting.The shape of silica support is typically using spherical, the mm of its particle diameter 0.1 mm ~ 0.5.The carrier of described amorphous silica-alumina cladding silica can be prepared using rolling balling method, and method is as follows：Silica support is put into bowling machine, amorphous silica-alumina dry powder is equably sprinkled into rolling process and binding agent is sprayed into, carrier is constantly grown up.Carrier after balling-up is finished dries the h of 3 h ~ 24 at 30 DEG C ~ 50 DEG C, is then calcined 2 h ~ 6 at 400 DEG C ~ 700 DEG C
h.Siliconoxide mass content is 15 % ~ 50 in described amorphous silica-alumina
%.Described binding agent is that mass concentration is 5 % ~ 10
One or more in % dilute acid soln, such as acetic acid, nitric acid.The addition of binding agent is 0.5 ~ 1.5 with the mass ratio of amorphous silica-alumina dry powder.
The property of described silica support is as follows：Specific surface area is 500 ~ 820
m2/ g, pore volume is 0.62 ~ 0.92 mL/g, and average pore diameter is 4.6 ~ 6.6 nm.The preferred preparation method of described silica support is as follows：
A, template is added in the aqueous solution of organic acid, obtains solution I；
B, silicon source is added in solution I, then at 60 DEG C ~ 90 DEG C stirring into gel；
Gel obtained by C, step B is dried and is calcined, silica support is made through aging.
In step A, the organic acid is SiO in the one or more in citric acid, tartaric acid, malic acid, described organic acid and carrier2Mol ratio be 0.1 ~ 1.2.
In step A, the template is SiO in the one or more in the polyethylene glycol that cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, lauryl sodium sulfate, triblock polymer P123, triblock polymer F127, triblock polymer F108, molecular weight are 1000 ~ 10000, described template and carrier2Mol ratio be 0.01 ~ 1.2.
In step B, described silicon source is the one or more in tetraethyl orthosilicate, Ludox.
In step C, described silica support can add binding agent and shaping assistant as needed in forming process, and binding agent typically uses small porous aluminum oxide.Shaping assistant such as peptizing agent, extrusion aid etc..
In step C, described drying and roasting is carried out using usual manner, dries the condition typically used as follows:90 DEG C ~ 120 DEG C dry 3h ~ 12h, roasting is general to be calcined the h of 2 h ~ 6 at 300 DEG C ~ 800 DEG C.
Step（2）In, the method that auxiliary agent nickel and iron are loaded on carrier can be using conventional infusion process, such as saturation infusion process.After immersion, using conventional drying and roasting process, drying condition is as follows：In 90 DEG C ~ 120 DEG C dry 3h ~ 12h, roasting condition is as follows：The h of 2 h ~ 6 is calcined at 300 DEG C ~ 500 DEG C.Step（3）In, nickel source can be using soluble nickel salt, the generally one or more in nickel nitrate, nickel acetate.Source of iron can be using soluble molysite, the generally one or more in ferric nitrate, ferric sulfate, iron chloride.
Step（3）In, described reduction treatment process is as follows：Catalyst precarsor is warming up to 300 DEG C~600 DEG C under hydrogen atmosphere, 4h~8h is handled under 0.1MPa~0.5MPa.Wherein reduction treatment can use pure hydrogen, it would however also be possible to employ the hydrogen containing inert gas, and hydrogen volume concentration is 30% ~ 100%.
Step（4）In, described polyalcohol is the one or more in C5~C10 polyalcohols, the preferably one or more in xylitol, sorbierite, mannitol, arabite；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably 5%~30%, the addition and step of polyalcohol and/or furfural（1）The mass ratio of the catalyst carrier of gained is 2:1~10:1, preferably 3:1~10:1.
Step（5）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid and the mass ratio of carrier are 0.1 ~ 0.4.
Step（6）Described heating stirring is general to be carried out at 40 DEG C ~ 90 DEG C.
Step（7）In, by step（6）Obtained catalyst precarsor C, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is generally the min of 5 min ~ 30.By step（6）Obtained solid absorption ammonia, adsorption time is generally the min of 5 min ~ 30.Step（7）In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
Step（7）In, described ammonia can use pure ammonia, it would however also be possible to employ in the gaseous mixture containing ammonia, mixed gas in addition to ammonia, and other is the one or more in inert gas such as nitrogen, argon gas.
Step（8）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
Step（8）Described heating stirring is general to be carried out at 40 DEG C ~ 90 DEG C.
Step（8）Described in dry and roasting condition it is as follows：90 DEG C ~ 120
DEG C the h of 3 h ~ 12 is dried, 2 h ~ 6 are calcined at 300 DEG C ~ 550 DEG C
h。
Present invention also offers a kind of method of producing ethylene by ethanol dehydration, wherein using the catalyst of the present invention.Catalyst of the present invention be particularly suitable for use in the low-concentration ethanol aqueous solution be raw material dehydration it is ethylene reaction produced, using fixed-bed process, the reaction condition of described preparing ethylene by dehydrating ethanol is as follows：Ethanol water concentration is 5wt% ~ 40wt%, the h of mass space velocity 0.5-1~15.0 h-1, 160 DEG C ~ 400 DEG C of reaction temperature.
Compared with prior art, catalyst of the present invention has advantages below and feature：
（1）In catalyst of the present invention, silicon oxide surface coats appropriate amorphous silica-alumina, can increase its specific surface area, aperture and pore volume, can load more ammonium heteropoly acidses, so not but not change silica support overall pore structure, and be conducive to improve catalyst total acid content；
（2）Catalyst of the present invention coats silica support, the addition of auxiliary agent iron, it is possible to increase the acidity of carrier using amorphous silica-alumina, acidity especially in duct, and hydrogenation is played jointly with auxiliary agent nickel, and catalytic polyol and/or furfural liquid-phase hydrogenatin in autoclave mainly there are two aspect effects：One is the liquid alkane absorption of polyalcohol and/or furfural liquid-phase hydrogenatin generation is on a catalyst support, the duct of carrier can be effectively blocked, the heteropoly acid ammonium subsequently loaded is distributed on carrier outer surface；On the other hand, polyalcohol and/or furfural liquid-phase hydrogenatin can produce carbon distribution on carrier, the acidity of carrier can be weakened to a certain extent, reduce the quantity of support acidity position absorption ammonia, heteropoly acid is set mainly to be reacted with ammonium salt organic acid generation ammonium heteropoly acidses, contribute to ammonium heteropoly acidses dispersed in carrier surface, and above-mentioned carbon deposit can be removed through follow-up high-temperature roasting, so effectively remain this Component Vectors acidic site.The catalyst that the inventive method is obtained not only has the characteristics of low temperature active is high, selectivity is good, carbon accumulation resisting ability is strong, and good stability.
Embodiment
With reference to embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
（1）The preparation of carrier：
Weigh 145.8g cetyl trimethylammonium bromides and 205g citric acids are made into mixed solution, 302mL tetraethyl orthosilicates are added in mixed solution, stir 2 h, then at 70 DEG C stirring into gel, by gel at 40 DEG C the h of aging 12, then 8 h are dried at 110 DEG C, particle diameter is made for 0.4mm spherical silicas, is calcined 3 h at 580 DEG C, obtains silica support, wherein the mol ratio of cetyl trimethylammonium bromide and silica is 0.3, and the mol ratio of citric acid and silica is 0.8.Support is：Specific surface area is 525 m2/ g, pore volume is 0.64 mL/g, and average pore diameter is 4.9 nm.
The particle diameter prepared is added in bowling machine for 0.4mm spherical silicas, bowling machine is started, amorphous silica-alumina dry powder is equably sprinkled into machine（In terms of butt, silica content 20wt%）, while spraying into the acetic acid aqueous solution that mass concentration is 6%, after balling-up is finished, carrier is dried into 12 h at 40 DEG C, then 3 h are calcined at 500 DEG C, the silica support of amorphous silica-alumina cladding is obtained, wherein amorphous silica-alumina accounts for the 20% of silica weight.
（2）The preparation of catalyst：
Weigh the carrier 74g prepared to be added in the mixed aqueous solution containing 31.1g nickel nitrates and 15.2g ferric nitrates, stir to solution and be evaporated at 70 DEG C, obtained material is calcined 3h in 110 DEG C of dry 8h at 400 DEG C, and catalyst precarsor A is made.Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, the sorbitol solution that 400g mass concentrations are 20% is added, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is come out, dried at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 11.1g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 40 DEG C；It is then added in the aqueous solution containing 15.6g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 500 DEG C, catalyst are made, wherein NiO contents are 8wt%, Fe2O3Content is 3wt%, (NH4)0.5H2.5PW12O40Content is 15wt%.
（3）Catalyst characterization：
Taken a little in the surrounding in catalyst granules section and centre, elementary analysis is carried out to each point by SEM, as a result shown：Heteropoly acid ammonium salt content at surrounding each point is substantially suitable, and middle each point is not detected by ammonium heteropoly acidses, illustrates the catalyst prepared using the method, it is scattered that ammonium heteropoly acidses have had on catalyst surface, and is not impregnated with into duct.
（4）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20% ethanol water, mass space velocity 4h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts after reacting 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 2
（1）The preparation of carrier：
Weigh 200g cetyl trimethylammonium bromides and 105.7g citric acids are made into mixed solution, 250mL tetraethyl orthosilicates are added in mixed solution, stir 2 h, then at 70 DEG C stirring into gel, by gel at 40 DEG C the h of aging 12, then 8 h are dried at 110 DEG C, particle diameter is made for 0.3mm spherical silicas, is calcined 3 h at 600 DEG C, obtains silica support, wherein the mol ratio of cetyl trimethylammonium bromide and silica is 0.5, and the mol ratio of citric acid and silica is 0.5.Support is：Specific surface area is 570 m2/ g, pore volume is 0.72 mL/g, and average pore diameter is 5.1 nm.
The particle diameter prepared is added in bowling machine for 0.3mm spherical silicas, bowling machine is started, amorphous silica-alumina dry powder is equably sprinkled into machine（In terms of butt, silica content 30wt%）, while spraying into the acetic acid aqueous solution that mass concentration is 6%, after balling-up is finished, carrier is dried into 12 h at 40 DEG C, then 3 h are calcined at 500 DEG C, the silica support of amorphous silica-alumina cladding is obtained, wherein amorphous silica-alumina accounts for the 30% of silica weight.
（2）The preparation of catalyst：
Weigh the carrier 63g prepared to be added in the mixed aqueous solution containing 46.7g nickel nitrates and 25.3g ferric nitrates, stir to solution and be evaporated at 70 DEG C, obtained material is calcined 3h in 110 DEG C of dry 8h at 400 DEG C, and catalyst precarsor A is made.Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, the furfuryl aldehyde solution that 400g mass concentrations are 20% is added, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 150 DEG C, after reaction terminates, catalyst filtration is come out, dried at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 15.8g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 40 DEG C；It is then added in the aqueous solution containing 20.7g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 470 DEG C, catalyst are made, wherein NiO contents are 12wt%, Fe2O3Content is 5wt%, (NH4)0.7H2.3PW12O40Content is 20wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20% ethanol water, mass space velocity 5h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts after reacting 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 3
（1）The preparation of carrier：
Weigh 316g cetyl trimethylammonium bromides and 62.4g citric acids are made into mixed solution, 246mL tetraethyl orthosilicates are added in mixed solution, stir 2 h, then at 70 DEG C stirring into gel, by gel at 40 DEG C the h of aging 12, then 8 h are dried at 110 DEG C, particle diameter is made for 0.2mm spherical silicas, is calcined 3 h at 650 DEG C, obtains silica support, wherein the mol ratio of cetyl trimethylammonium bromide and silica is 0.8, and the mol ratio of citric acid and silica is 0.3.Support is：Specific surface area is 630 m2/ g, pore volume is 0.81 mL/g, and average pore diameter is 5.1 nm.
The particle diameter prepared is added in bowling machine for 0.2mm spherical silicas, bowling machine is started, amorphous silica-alumina dry powder is equably sprinkled into machine（In terms of butt, silica content 40wt%）, while spraying into the acetic acid aqueous solution that mass concentration is 6%, after balling-up is finished, carrier is dried into 12 h at 40 DEG C, then 3 h are calcined at 500 DEG C, the silica support of amorphous silica-alumina cladding is obtained, wherein amorphous silica-alumina accounts for the 40% of silica weight.
（2）The preparation of catalyst：
Weigh the carrier 53g prepared to be added in the mixed aqueous solution containing 58.4g nickel nitrates and 35.4g ferric nitrates, stir to solution and be evaporated at 70 DEG C, obtained material is calcined 3h in 110 DEG C of dry 8h at 400 DEG C, and catalyst precarsor A is made.Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, 4h is handled under 0.3MPa, reaction temperature is down to, the sorbitol solution that 400g mass concentrations are 20% is added, Hydrogen Vapor Pressure is then adjusted to 3MPa, 3h is reacted at 260 DEG C, after reaction terminates, catalyst filtration is come out, dried at room temperature to carrier surface without liquid phase；It is then added in the aqueous solution containing 18.6g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 40 DEG C；It is then added in the aqueous solution containing 25.9g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 520 DEG C, catalyst are made, wherein NiO contents are 15wt%, Fe2O3Content is 7wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
（3）The evaluation of catalyst：
Evaluating catalyst is carried out in atmospheric fixed bed tubular reactor, and raw material is 20% ethanol water, mass space velocity 8h-1, 240 DEG C of reaction temperature.Before reaction, catalyst is in N22 h are activated in 400 DEG C under protection, reaction temperature is then down to and starts after reacting 4 hours, product is analyzed by gas-chromatography, is calculated ethanol conversion and ethylene selectivity, be the results are shown in Table 1.
Embodiment 4
Catalyst is made according to embodiment 3, is tested according to the estimation of stability that the appreciation condition of embodiment 3 has carried out 100 h to catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 2.
Comparative example 1
In embodiment 3, carrier is added directly into the mixed aqueous solution containing 58.4g nickel nitrates, 35.4g ferric nitrates and 25.9g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 350 DEG C, catalyst are made, wherein NiO contents are 15wt%, Fe2O3Content is 7wt%, H3PW12O40Content is 25wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 2
In embodiment 3, the consumption of adjustment silica and amorphous silica-alumina, makes amorphous silica-alumina account for the 5% of silica weight, remaining be the same as Example 3, and catalyst is made, and NiO contents are 15wt%, Fe2O3Content is 7wt%, H3PW12O40Content is 25wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 3
In embodiment 3, the consumption of silica and amorphous silica-alumina will be adjusted, amorphous silica-alumina is accounted for the 70% of silica weight, catalyst is made in remaining be the same as Example 3, and NiO contents are 15wt%, Fe2O3Content is 7wt%, H3PW12O40Content is 25wt%,
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 4
In embodiment 3, catalyst precarsor A is added in C6 alkane solvents, impregnates 10min, then filter, dried at 40 DEG C to carrier surface without liquid phase；It is then added in the aqueous solution containing 18.6g citric acids, stirs to solution and be evaporated at 40 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, is dried after filtering at 40 DEG C；It is then added in the aqueous solution containing 25.9g phosphotungstic acids, stirs to solution and be evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, 3.0 h then are calcined at 520 DEG C, catalyst are made, wherein NiO contents are 15wt%, Fe2O3Content is 7wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
The evaluation be the same as Example 3 of catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 1.
Comparative example 5
Catalyst is made according to comparative example 1, is tested according to the estimation of stability that the appreciation condition of embodiment 3 has carried out 100 h to catalyst, ethanol conversion and ethylene selectivity the results are shown in Table 2.
The conversion ratio and selectivity of 1 each catalyst of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 1 | 98.5 | 98.8 |
| Embodiment 2 | 98.6 | 98.7 |
| Embodiment 3 | 99.2 | 99.0 |
| Comparative example 1 | 98.0 | 96.0 |
| Comparative example 2 | 95.4 | 94.6 |
| Comparative example 3 | 96.2 | 95.4 |
| Comparative example 4 | 97.0 | 96.8 |
The stability test evaluation result of table 2
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 4 | 99.0 | 98.8 |
| Comparative example 5 | 86.1 | 85.0 |
From Tables 1 and 2 result, activity, selectivity and the stability of catalyst of the present invention are significantly better than comparative example catalyst.
Claims (15)
1. a kind of heteropoly acid ammonium salt catalyst, including active component, auxiliary agent and carrier, active component are shown in formula for ammonium heteropoly acidses（1）, auxiliary agent is nickel oxide and di-iron trioxide, and carrier is the silica that amorphous silica-alumina is coated；The weight of amorphous silica-alumina accounts for the 15% ~ 45% of vehicle weight, preferably 16% ~ 40%；On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 8% ~ 30%, and auxiliary agent is in terms of oxide, and the content of nickel oxide is 3% ~ 18%, and the content of di-iron trioxide is 1% ~ 10%, and the content of carrier is 42% ~ 88%；Preferably：On the basis of the weight of catalyst, the content of ammonium heteropoly acidses is 12% ~ 25%, and auxiliary agent is in terms of oxide, and the content of nickel oxide is 5% ~ 15%, and the content of di-iron trioxide is 2% ~ 7%, and the content of carrier is 53% ~ 81%；
Hm(NH4)nYX12O40（1）
Wherein X represents W or Mo, Y represent Si or P；When Y represents Si, m+n=4, n values are 0.1 ~ 1.0；When Y represents P, m+n=3, n values are 0.1 ~ 1.0.
2. according to the catalyst described in claim 1, it is characterised in that：In described heteropoly acid ammonium salt catalyst, ammonium heteropoly acidses are distributed in the outer surface of carrier.
3. according to the catalyst described in claim 1, it is characterised in that：In described amorphous silica-alumina, the mass content of silica is 15% ~ 50%.
4. the preparation method of any described catalyst of claims 1 to 3, including：
（1）Prepare the carrier that amorphous silica-alumina coats silica；
（2）Auxiliary agent nickel and iron are loaded into step（1）On the carrier of preparation, catalyst precarsor A is obtained；
（3）Catalyst precarsor A is added in autoclave, reduction treatment is carried out to it using hydrogen；
（4）Polyalcohol and/or furfuryl aldehyde solution are driven into autoclave, Hydrogen Vapor Pressure is then adjusted to 2~4MPa, 0.5~5.0h is reacted at 100~300 DEG C；
（5）By step（4）In reacted catalyst precarsor A filter out, be dried at room temperature, until sample surfaces are without liquid phase, obtain catalyst precarsor B；
（6）By step（5）Obtained catalyst precarsor B is added in aqueous solutions of organic acids, and heating stirring to solution is evaporated, and obtains catalyst precarsor C；
（7）By step（6）Obtained catalyst precarsor C is added in the alkaline solution containing ammonium, through filtering, is dried at 40 DEG C ~ 90 DEG C；Or by step（6）Obtained material adsorbs ammonia at 40 DEG C ~ 90 DEG C, obtains catalyst precarsor D；
（8）The aqueous solution of heteropoly acid is added to step（7）In obtained catalyst precarsor D, heating stirring to solution is evaporated, then through drying and being calcined, produces catalyst.
5. in accordance with the method for claim 4, it is characterised in that：Step（1）In, the preparation method for the carrier that described amorphous silica-alumina coats silica is as follows：Silica support is first prepared, is then formed again with amorphous silica-alumina cladding, the property of described silica support is as follows：Specific surface area is 500 ~ 820 m2/ g, pore volume is 0.62 ~ 0.92 mL/g, and average pore diameter is 4.6 ~ 6.6 nm.
6. in accordance with the method for claim 5, it is characterised in that：Silica support is obtained by silica rubber powder through shaping, dry and roasting, and the shape of silica support uses spherical, its particle diameter 0.1
mm~0.5 mm；The carrier of described amorphous silica-alumina cladding silica is prepared using rolling balling method, and method is as follows：Silica support is put into bowling machine, amorphous silica-alumina dry powder is equably sprinkled into rolling process and binding agent is sprayed into, carrier is constantly grown up, the carrier after balling-up is finished dries the h of 3 h ~ 24 at 30 DEG C ~ 50 DEG C, the h of 2 h ~ 6 is then calcined at 400 DEG C ~ 700 DEG C；Described binding agent is the dilute acid soln that mass concentration is the % of 5 % ~ 10；The addition of binding agent is 0.5 ~ 1.5 with the mass ratio of amorphous silica-alumina dry powder.
7. in accordance with the method for claim 5, it is characterised in that：Step（2）In, the method that auxiliary agent nickel and iron are loaded on carrier uses infusion process, after immersion, as follows with roasting condition using drying：In 90 DEG C ~ 120 DEG C dry 3h ~ 12h, roasting condition is as follows：The h of 2 h ~ 6 is calcined at 300 DEG C ~ 500 DEG C.
8. in accordance with the method for claim 5, it is characterised in that：Step（3）In, described reduction treatment process is as follows：Catalyst precarsor is warming up to 300 DEG C~600 DEG C under hydrogen atmosphere, 4h~8h is handled under 0.1MPa~0.5MPa.
9. in accordance with the method for claim 5, it is characterised in that：Step（4）In, described polyalcohol is the one or more in C5~C10 polyalcohols；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably 5%~30%, the addition and step of polyalcohol and/or furfural（1）The mass ratio of the catalyst carrier of gained is 2:1~10:1, preferably 3:1~10:1.
10. in accordance with the method for claim 5, it is characterised in that：Step（5）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid, and described organic acid and the mass ratio of carrier are 0.1 ~ 0.4.
11. in accordance with the method for claim 5, it is characterised in that：Step（7）In, by step（6）Obtained catalyst precarsor C, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is the min of 5 min ~ 30；By step（6）Obtained solid absorption ammonia, adsorption time is the min of 5 min ~ 30；Step（7）In, the alkaline solution containing ammonium is the one or more in ammoniacal liquor, sal volatile, ammonium bicarbonate soln.
12. in accordance with the method for claim 5, it is characterised in that：Step（8）In, described heteropoly acid is the one or more in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid.
13. in accordance with the method for claim 5, it is characterised in that：Step（8）Described in dry and roasting condition it is as follows：In the h of 90 DEG C ~ 120 DEG C 3 h of drying ~ 12, the h of 2 h ~ 6 is calcined at 300 DEG C ~ 550 DEG C.
14. a kind of method of producing ethylene by ethanol dehydration, it is characterised in that using any described catalyst of Claims 1 to 4.
15. in accordance with the method for claim 14, it is characterised in that：The method of producing ethylene by ethanol dehydration uses fixed-bed process, and the reaction condition of described preparing ethylene by dehydrating ethanol is as follows：Ethanol water concentration is 5wt% ~ 40wt%, the h of mass space velocity 0.5-1~15.0 h-1, 160 DEG C ~ 400 DEG C of reaction temperature.
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| CN109046410A (en) * | 2018-09-29 | 2018-12-21 | 盐城工学院 | A kind of double activated catalyst of heavy aromatic hydrocarbon light and its preparation method and application |
| CN109926092A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | Heteropoly acid ammonium salt catalyst and its preparation method |
| CN114700069A (en) * | 2022-04-07 | 2022-07-05 | 新兴能源科技有限公司 | Preparation method and application of catalyst for preparing ethylene by ethanol dehydration |
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| US20110060158A1 (en) * | 2009-09-08 | 2011-03-10 | Lg Chem, Ltd. | Preparation Method for (Meth)acrylate |
| CN105646130A (en) * | 2014-12-02 | 2016-06-08 | 中国石油化工股份有限公司 | Method for preparation of ethylene by ethanol dehydration |
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| US20110060158A1 (en) * | 2009-09-08 | 2011-03-10 | Lg Chem, Ltd. | Preparation Method for (Meth)acrylate |
| CN105646130A (en) * | 2014-12-02 | 2016-06-08 | 中国石油化工股份有限公司 | Method for preparation of ethylene by ethanol dehydration |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109926092A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | Heteropoly acid ammonium salt catalyst and its preparation method |
| CN109926092B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Heteropolyacid ammonium salt catalyst and preparation method thereof |
| CN109046410A (en) * | 2018-09-29 | 2018-12-21 | 盐城工学院 | A kind of double activated catalyst of heavy aromatic hydrocarbon light and its preparation method and application |
| CN109046410B (en) * | 2018-09-29 | 2021-03-12 | 盐城工学院 | Double-activity catalyst for light conversion of heavy aromatic hydrocarbon and preparation method and application thereof |
| CN114700069A (en) * | 2022-04-07 | 2022-07-05 | 新兴能源科技有限公司 | Preparation method and application of catalyst for preparing ethylene by ethanol dehydration |
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