CN106944139B - 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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- CN106944139B CN106944139B CN201610003172.3A CN201610003172A CN106944139B CN 106944139 B CN106944139 B CN 106944139B CN 201610003172 A CN201610003172 A CN 201610003172A CN 106944139 B CN106944139 B CN 106944139B
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- catalyst
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- silica
- acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 28
- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 109
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000005977 Ethylene Substances 0.000 claims abstract description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 150000007513 acids Chemical class 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 12
- 238000005253 cladding Methods 0.000 claims abstract description 9
- 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 150000005846 sugar alcohols Polymers 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 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 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 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
- 239000011148 porous material Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000007921 spray Substances 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
- 229910003978 SiClx Inorganic materials 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
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005096 rolling process Methods 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
- 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
- 229920001971 elastomer Polymers 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 2
- 230000037396 body weight Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004939 coking Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 235000015165 citric acid Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 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 10
- 239000000463 material Substances 0.000 description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid 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
- 230000032683 aging Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 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
- 238000000465 moulding Methods 0.000 description 2
- 239000003921 oil Substances 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
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- -1 ammonium salt organic acid Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 230000008859 change Effects 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
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 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
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000005259 measurement Methods 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
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 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
- 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
-
- 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
-
- 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
Landscapes
- 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 catalysts and preparation method thereof.The catalyst includes active component, auxiliary agent and carrier, and active component is ammonium heteropoly acids, and auxiliary agent is nickel oxide and di-iron trioxide, and carrier is the silica of amorphous silica-alumina cladding.While catalyst of the present invention low temperature active with higher, selectivity and coking resistivity, the stability of catalyst is improved.Catalyst of the present invention is ethylene reaction produced especially suitable for the dehydration that low-concentration ethanol aqueous solution is raw material.
Description
Technical field
The present invention relates to a kind of heteropoly acid ammonium salt catalysts and preparation method thereof, are used for ethanol dehydration more particularly to one kind
Produce the carried heteropoly acid ammonium salt in catalysis agent and preparation method thereof of ethylene.
Background technique
Flagship product of the ethylene as basic Organic Chemicals and petro chemical industry, about 75% chemical products
It is to be prepared by raw material of ethylene, therefore the size of ethylene yield has become one national oil development of chemical industry water of measurement
Flat important symbol.Traditional ethylene is mainly the heavy dependence petroleum resources as made from light petroleum fraction cracking.With
The day of international energy situation is becoming tight, and petroleum resources are increasingly exhausted, and developing new renewable alternative energy source has been the task of top priority.
Recently, ethyl alcohol especially recyclable organism preparing ethylene by dehydrating ethanol is increasingly valued by people, and is had
Green, sustainable, various advantages such as reaction condition is mild and product ethylene is with high purity.Bio-ethanol is mainly derived from agriculture
The fermentation of byproduct can avoid the dependence to petroleum resources, deficient in some petroleum resources such as Brazil, India, Pakistan
Country continues to use always this method production ethylene, and this point more has realistic meaning to the country of oil-poor and few oil.Ethanol dehydration prepares second
Alkene has the great potential for partly or entirely replacing obtaining ethylene from petroleum.Therefore, research producing ethylene from dehydration of ethanol has great
Economic value and strategic importance.
There are many catalyst for ethanol delydration to ethylene report, mainly activated alumina, molecular sieve and heteropoly acid etc..It is living
Property aluminium oxide is cheap as catalyst, and activity and selectivity is preferable, but reaction temperature is high, and reaction velocity is low, energy
Consumption is high, and utilization rate of equipment and installations is low.The catalytic activity and selectivity of molecular sieve are high, stablize；Reaction temperature is low, and reaction velocity is big, but
Catalyst life is short, and amplification factor is small, limits its industrialized production.Heteropoly acid is by central atom and coordination atom with one
Fixed structure passes through oxygen-containing polyacid made of oxygen atom ligand bridging, has many advantages, such as highly acid.In producing ethylene from dehydration of ethanol
The characteristics of in reaction, heteropolyacid catalyst has reaction temperature low, selectivity height and high income.
CN201310509561.X discloses a kind of ZSM-5 molecular sieve catalyst that heteropoly acid is modified, is used for low concentration second
Dehydration of alcohols is ethylene reaction produced.Catalyst shows higher catalytic activity and selectivity, but due to the specific surface of carrier and
Aperture is relatively small, cannot load more heteropoly acids, and excessive heteropoly acid can block the duct of carrier, lead to catalyst activity
Decline, therefore further increasing which limit catalyst activity.
Li Benxiang etc. [Chemical Engineering Technology and exploitation, 2010,5 (39): 7-9] reports entitled MCM-41 load Catalyzed by Silicotungstic Acid
The article of producing ethylene from dehydration of ethanol, catalyst are prepared using infusion process.CN200910057539.X discloses a kind of ethanol dehydration
The catalyst of ethylene processed.For the catalyst using aluminium oxide as carrier, active component is heteropoly acid, is prepared using kneading method.It is above-mentioned to urge
Agent shows higher catalytic activity and selectivity when using high concentration ethanol as raw material, but working as with low-concentration ethanol is original
When material, catalyst activity is decreased obviously, and stability is bad.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of heteropoly acid ammonium salt catalyst and its preparations
Method.The catalyst not only has the characteristics that low temperature active is high, selectivity is good, has strong anti-carbon capacity, and stability is good.
Heteropoly acid ammonium salt catalyst of the present invention, including active component, auxiliary agent and carrier, active component are shown in for ammonium heteropoly acids
Formula (1), auxiliary agent are nickel oxide and di-iron trioxide, and carrier is the silica of amorphous silica-alumina cladding；The weight of amorphous silica-alumina
Account for the 15% ~ 45% of vehicle weight, preferably 16% ~ 40%；On the basis of the weight of catalyst, the contents of ammonium heteropoly acids is 8% ~
30%, preferably 12% ~ 25%, auxiliary agent is in terms of oxide, and the content of nickel oxide is 3% ~ 18%, preferably 5% ~ 15%, di-iron trioxide
Content be 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, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P
When, m+n=3, n value is 0.1 ~ 1.0.
In the heteropoly acid ammonium salt catalyst, ammonium heteropoly acids are distributed in the outer surface of carrier.
The preparation method of the heteropoly acid ammonium salt catalyst, comprising:
(1) carrier of amorphous silica-alumina cladding silica is prepared；
(2) auxiliary agent nickel and iron are loaded on the carrier of step (1) preparation, obtains catalyst precarsor A；
(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, then adjusting Hydrogen Vapor Pressure to 2~4MPa,
0.5~5.0h is reacted at 100~300 DEG C；
(5) the catalyst precarsor A after reaction in step (4) is filtered out, is dried at room temperature, until sample table
Face obtains catalyst precarsor B without liquid phase；
(6) the catalyst precarsor B that step (5) obtains being added in aqueous solutions of organic acids, heating stirring to solution is evaporated,
Obtain catalyst precarsor C；
(7) the catalyst precarsor C that step (6) obtains is added in the alkaline solution containing ammonium, through filtering, 40 DEG C ~ 90
It is dry at DEG C；Or the material that step (6) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(8) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (7) obtains, heating stirring to solution is steamed
It is dry, then through dry and roasting to get catalyst.
In step (1), the carrier of the amorphous silica-alumina cladding silica can be prepared by conventional method.In the present invention
It is preferred that preparing with the following method: first preparing silica support, then coated again with amorphous silica-alumina.Wherein silica carries
Body can be obtained by silica rubber powder through molding, drying and roasting.The shape of silica support generally uses spherical shape, partial size 0.1
mm~0.5 mm.The preparation of rolling balling method can be used in the carrier of the amorphous silica-alumina cladding silica, the method is as follows: by oxygen
SiClx carrier is put into bowling machine, is equably sprinkled into amorphous silica-alumina dry powder during scrolling and is sprayed into binder, makes carrier
Constantly grow up.Carrier after balling-up dries the h of 3 h ~ 24 at 30 DEG C ~ 50 DEG C, then in 400 DEG C ~ 700 DEG C 2 h of roasting
~6 h.Siliconoxide mass content is the % of 15 % ~ 50 in the amorphous silica-alumina.The binder be mass concentration be 5 % ~
The dilute acid soln of 10 %, such as one of acetic acid, nitric acid or a variety of.The additional amount of binder and the quality of amorphous silica-alumina dry powder
Than being 0.5 ~ 1.5.
The property of the silica support is as follows: specific surface area is 500 ~ 820 m20.62 ~ 0.92 mL/ of/g, Kong Rongwei
G, average pore diameter are 4.6 ~ 6.6 nm.The silica support preferred the preparation method 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, is then stirred at 60 DEG C ~ 90 DEG C at gel；
C, silica support is made through aging, dry and roasting in the resulting gel of step B.
In step A, the organic acid be one of citric acid, tartaric acid, malic acid or a variety of, the organic acid with
SiO in carrier2Molar ratio be 0.1 ~ 1.2.
In step A, the template is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecane
Base sodium sulphate, triblock polymer P123, triblock polymer F127, triblock polymer F108, molecular weight be 1000 ~
One of 10000 polyethylene glycol is a variety of, SiO in the template and carrier2Molar ratio be 0.01 ~ 1.2.
In step B, the silicon source is one of ethyl orthosilicate, silica solution or a variety of.
In step C, the silica support can according to need addition binder and molding help in forming process
Agent, binder generally use small porous aluminum oxide.Shaping assistant such as peptizing agent, extrusion aid etc..
In step C, the drying and roasting are carried out using usual manner, and the dry condition generally used is as follows: 90 DEG C
~ 120 DEG C of dry 3h ~ 12h are roasted generally in 300 DEG C ~ 800 DEG C roasting 2 h ~ 6 h.
In step (2), auxiliary agent nickel and iron are loaded to the method on carrier can be using conventional infusion process, for example is saturated
Infusion process.After immersion, as follows using conventional drying and roasting process, drying condition: 90 DEG C ~ 120 DEG C dry 3h ~
12h, roasting condition are as follows: in 300 DEG C ~ 500 DEG C roasting 2 h ~ 6 h.In step (3), nickel source can use soluble nickel salt,
Generally one of nickel nitrate, nickel acetate or a variety of.Source of iron can be using soluble molysite, generally ferric nitrate, sulfuric acid
One of iron, iron chloride are a variety of.
In step (3), the reduction treatment process is as follows: under hydrogen atmosphere by catalyst precarsor be warming up to 300 DEG C~
600 DEG C, 4h~8h is handled at 0.1MPa~0.5MPa.Wherein reduction treatment can use pure hydrogen, can also be using containing lazy
Property gas hydrogen, hydrogen volume concentration be 30% ~ 100%.
In step (4), the polyalcohol is one of C5~C10 polyalcohol or a variety of, preferably xylitol, sorb
One of alcohol, mannitol, arabite are a variety of；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, preferably
It is 5%~30%, the additional amount of polyalcohol and/or furfural and the mass ratio of step (1) resulting catalyst carrier are 2:1 ~ 10:1,
Preferably 3:1 ~ 10:1.
In step (5), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
Mass ratio with carrier is 0.1 ~ 0.4.
Heating stirring described in step (6) generally carries out at 40 DEG C ~ 90 DEG C.
In step (7), the catalyst precarsor C that step (6) obtains is added in the alkaline solution containing ammonium and is impregnated, soaked
The stain time is generally the min of 5 min ~ 30.The solid absorption ammonia that step (6) is obtained, adsorption time are generally 5 min ~ 30
min.In step (7), the alkaline solution containing ammonium is one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or more
Kind.
In step (7), pure ammonia is can be used in the ammonia, the gaseous mixture containing ammonia can also be used, in mixed gas
It is other for one of inert gas such as nitrogen, argon gas etc. or a variety of in addition to ammonia.
In step (8), the heteropoly acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
Heating stirring described in step (8) generally carries out at 40 DEG C ~ 90 DEG C.
Dry and roasting condition described in step (8) is as follows: in 90 DEG C ~ 120 DEG C drying h of 3 h ~ 12,300 DEG C ~
550 DEG C of roasting 2 h ~ 6 h.
The present invention also provides a kind of methods of producing ethylene by ethanol dehydration, wherein using catalyst of the invention.This hair
Bright catalyst is ethylene reaction produced especially suitable for the dehydration that low-concentration ethanol aqueous solution is raw material, described using fixed-bed process
Preparing ethylene by dehydrating ethanol reaction condition it is as follows: ethanol water concentration be 5wt% ~ 40wt%, 0.5 h of mass space velocity-1~
15.0 h-1, 160 DEG C ~ 400 DEG C of reaction temperature.
Compared with prior art, catalyst of the present invention has the following advantages that and feature:
(1) in catalyst of the present invention, silicon oxide surface coats suitable amorphous silica-alumina, can increase its specific surface area,
Aperture and Kong Rong, can load more ammonium heteropoly acids, not but not change the whole hole knot of silica support in this way
Structure, and be conducive to improve the total acid content of catalyst；
(2) catalyst of the present invention coats silica support using amorphous silica-alumina, and the addition of auxiliary agent iron can be improved carrier
Acidity, the especially acidity in duct, and play hydrogenation jointly with auxiliary agent nickel, the catalytic polyol in autoclave
And/or furfural liquid-phase hydrogenatin, mainly there are two aspect effects: one is the liquid alkane that polyalcohol and/or furfural liquid-phase hydrogenatin generate
Hydrocarbon adsorbs on a catalyst support, can effectively block the duct of carrier, the heteropoly acid ammonium of subsequent load is made to be distributed in carrier
On outer surface；On the other hand, polyalcohol and/or furfural liquid-phase hydrogenatin can generate carbon distribution on carrier, can be to a certain extent
Weaken the acidity of carrier, reduces the quantity of support acidity position absorption ammonia, heteropoly acid is made mainly to react with ammonium salt organic acid life
At ammonium heteropoly acids, it is evenly dispersed in carrier surface to facilitate ammonium heteropoly acids, and can be removed through subsequent high-temperature roasting
Carbon deposit is stated, effectively remains this Component Vectors acidic site in this way.The catalyst that the method for the present invention obtains not only has low temperature living
Property is high, selectivity is good, the characteristics of having strong anti-carbon capacity, and stability is good.
Specific embodiment
Below with reference to embodiment, the present invention is described in detail.In the present invention, wt% is mass fraction.
Embodiment 1
(1) preparation of carrier:
It weighs 145.8g cetyl trimethylammonium bromide and 205g citric acid is made into mixed solution, by the positive silicic acid of 302mL
Tetra-ethyl ester is added in mixed solution, stirs 2 h, and then stirring is extremely at gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, then dry 8 h at 110 DEG C, are made partial size as 0.4mm spherical silica and obtain silica in 580 DEG C of 3 h of roasting
Carrier, wherein the molar ratio of cetyl trimethylammonium bromide and silica is 0.3, and the molar ratio of citric acid and silica is
0.8.Support are as follows: specific surface area is 525 m20.64 mL/g of/g, Kong Rongwei, average pore diameter are 4.9 nm.
It is that 0.4mm spherical silica is added in bowling machine by the partial size prepared, starts bowling machine, uniformly into machine
Ground is sprinkled into amorphous silica-alumina dry powder (in terms of butt, silica content 20wt%), while it is water-soluble to spray into the acetic acid that mass concentration is 6%
Carrier after balling-up, is dried 12 h by liquid at 40 DEG C, then in 500 DEG C of 3 h of roasting, obtains amorphous silica-alumina cladding
Silica support, wherein amorphous silica-alumina accounts for the 20% of silica weight.
(2) preparation of catalyst:
The carrier 74g prepared is weighed to be added in the mixed aqueous solution containing 31.1g nickel nitrate and 15.2g ferric nitrate,
It stirs at 70 DEG C and is evaporated to solution, catalyst precarsor A is made in 400 DEG C of roasting 3h in 110 DEG C of dry 8h in obtained material.
Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, 4h is handled at 0.3MPa, is down to
The sorbitol solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa in reaction temperature, anti-at 260 DEG C
It answers 3h, after reaction, catalyst filtration is come out, dries at room temperature to carrier surface without liquid phase；Be then added to containing
In the aqueous solution of 11.1g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material, which is added in sal volatile, to be impregnated
10min is dry at 40 DEG C after filtering；It is then added in the aqueous solution containing 15.6g phosphotungstic acid, stirs at 70 DEG C to molten
Liquid is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 500 DEG C of 3.0 h of roasting, catalyst is made, wherein NiO contains
Amount is 8wt%, Fe2O3Content is 3wt%, (NH4)0.5H2.5PW12O40Content is 15wt%.
(3) catalyst characterization:
It is taken a little in the surrounding in catalyst granules section and centre, elemental analysis is carried out to each point by SEM, the results showed that
Heteropoly acid ammonium salt content at surrounding each point is substantially suitable, and ammonium heteropoly acids are not detected in intermediate each point, illustrates using this side
The catalyst of method preparation, the dispersion that ammonium heteropoly acids have had on catalyst surface, and be not impregnated with into duct.
(4) evaluation of catalyst:
Evaluating catalyst carries 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 N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning reaction 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) preparation of carrier:
It weighs 200g cetyl trimethylammonium bromide and 105.7g citric acid is made into mixed solution, by the positive silicic acid of 250mL
Tetra-ethyl ester is added in mixed solution, stirs 2 h, and then stirring is extremely at gel at 70 DEG C, the aging 12 at 40 DEG C by gel
H, then dry 8 h at 110 DEG C, are made partial size as 0.3mm spherical silica and obtain silica in 600 DEG C of 3 h of roasting
Carrier, wherein the molar ratio of cetyl trimethylammonium bromide and silica is 0.5, and the molar ratio of citric acid and silica is
0.5.Support are as follows: specific surface area is 570 m20.72 mL/g of/g, Kong Rongwei, average pore diameter are 5.1 nm.
It is that 0.3mm spherical silica is added in bowling machine by the partial size prepared, starts bowling machine, uniformly into machine
Ground is sprinkled into amorphous silica-alumina dry powder (in terms of butt, silica content 30wt%), while it is water-soluble to spray into the acetic acid that mass concentration is 6%
Carrier after balling-up, is dried 12 h by liquid at 40 DEG C, then in 500 DEG C of 3 h of roasting, obtains amorphous silica-alumina cladding
Silica support, wherein amorphous silica-alumina accounts for the 30% of silica weight.
(2) preparation of catalyst:
The carrier 63g prepared is weighed to be added in the mixed aqueous solution containing 46.7g nickel nitrate and 25.3g ferric nitrate,
It stirs at 70 DEG C and is evaporated to solution, catalyst precarsor A is made in 400 DEG C of roasting 3h in 110 DEG C of dry 8h in obtained material.
Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, 4h is handled at 0.3MPa, is down to
Reaction temperature, is added the furfuryl aldehyde solution that 400g mass concentration is 20%, then adjusts Hydrogen Vapor Pressure to 3MPa, reacts at 150 DEG C
3h after reaction comes out catalyst filtration, dries at room temperature to carrier surface without liquid phase；It is then added to containing 15.8g
In the aqueous solution of citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material, which is added in sal volatile, to be impregnated
10min is dry at 40 DEG C after filtering；It is then added in the aqueous solution containing 20.7g phosphotungstic acid, stirs at 70 DEG C to molten
Liquid is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 470 DEG C of 3.0 h of roasting, catalyst is made, wherein NiO contains
Amount is 12wt%, Fe2O3Content is 5wt%, (NH4)0.7H2.3PW12O40Content is 20wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries 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 N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning reaction 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) preparation of carrier:
It weighs 316g cetyl trimethylammonium bromide and 62.4g citric acid is made into mixed solution, by the positive silicic acid four of 246mL
Ethyl ester is added in mixed solution, stirs 2 h, then at 70 DEG C stirring at gel, by gel at 40 DEG C 12 h of aging,
Then dry 8 h at 110 DEG C, it is 0.2mm spherical silica that partial size, which is made, in 650 DEG C of 3 h of roasting, obtains silica load
Body, wherein the molar ratio of cetyl trimethylammonium bromide and silica is 0.8, and the molar ratio of citric acid and silica is 0.3.
Support are as follows: specific surface area is 630 m20.81 mL/g of/g, Kong Rongwei, average pore diameter are 5.1 nm.
It is that 0.2mm spherical silica is added in bowling machine by the partial size prepared, starts bowling machine, uniformly into machine
Ground is sprinkled into amorphous silica-alumina dry powder (in terms of butt, silica content 40wt%), while it is water-soluble to spray into the acetic acid that mass concentration is 6%
Carrier after balling-up, is dried 12 h by liquid at 40 DEG C, then in 500 DEG C of 3 h of roasting, obtains amorphous silica-alumina cladding
Silica support, wherein amorphous silica-alumina accounts for the 40% of silica weight.
(2) preparation of catalyst:
The carrier 53g prepared is weighed to be added in the mixed aqueous solution containing 58.4g nickel nitrate and 35.4g ferric nitrate,
It stirs at 70 DEG C and is evaporated to solution, catalyst precarsor A is made in 400 DEG C of roasting 3h in 110 DEG C of dry 8h in obtained material.
Catalyst precarsor A is added in autoclave, 400 DEG C are warming up under hydrogen atmosphere, 4h is handled at 0.3MPa, is down to
The sorbitol solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa in reaction temperature, anti-at 260 DEG C
It answers 3h, after reaction, catalyst filtration is come out, dries at room temperature to carrier surface without liquid phase；Be then added to containing
In the aqueous solution of 18.6g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material, which is added in sal volatile, to be impregnated
10min is dry at 40 DEG C after filtering；It is then added in the aqueous solution containing 25.9g phosphotungstic acid, stirs at 70 DEG C to molten
Liquid is evaporated；By obtained solid in 110 DEG C of dry 8.0 h, then in 520 DEG C of 3.0 h of roasting, catalyst is made, wherein NiO contains
Amount is 15wt%, Fe2O3Content is 7wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
(3) evaluation of catalyst:
Evaluating catalyst carries 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 N2In 400 DEG C of 2 h of activation under protection, then it is down to reaction temperature and opens
After beginning reaction 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, has carried out the stabilization of 100 h to catalyst according to the evaluation condition of embodiment 3
Property evaluation experimental, ethanol conversion and ethylene selectivity the results are shown in Table 2.
Comparative example 1
In embodiment 3, carrier is added directly into containing 58.4g nickel nitrate, 35.4g ferric nitrate and 25.9g phosphotungstic acid
Mixed aqueous solution in, stirring is evaporated to solution at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, then 350
DEG C roasting 3.0 h, be made catalyst, wherein NiO content be 15wt%, Fe2O3Content is 7wt%, H3PW12O40Content is 25wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 2
In embodiment 3, the dosage for adjusting silica and amorphous silica-alumina, makes amorphous silica-alumina account for silica weight
5%, catalyst is made with embodiment 3 in remaining, and NiO content is 15wt%, Fe2O3Content is 7wt%, H3PW12O40Content is
25wt%。
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 3
In embodiment 3, the dosage that will adjust silica and amorphous silica-alumina, makes amorphous silica-alumina account for silica weight
70%, catalyst is made with embodiment 3 in remaining, and NiO content is 15wt%, Fe2O3Content is 7wt%, H3PW12O40Content is
25wt%,
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 4
In embodiment 3, catalyst precarsor A is added in C6 alkane solvent, impregnates 10min, then filters, at 40 DEG C
Lower drying is to carrier surface without liquid phase；It is then added in the aqueous solution containing 18.6g citric acid, stirs at 40 DEG C to solution
It is evaporated；Obtained material, which is added in sal volatile, impregnates 10min, dry at 40 DEG C after filtering；Be then added to containing
In the aqueous solution of 25.9g phosphotungstic acid, stirring to solution is evaporated at 70 DEG C；By obtained solid in 110 DEG C of dry 8.0 h, so
Afterwards in 520 DEG C of 3.0 h of roasting, catalyst is made, wherein NiO content is 15wt%, Fe2O3Content is 7wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.
The evaluation of catalyst the results are shown in Table 1 with embodiment 3, ethanol conversion and ethylene selectivity.
Comparative example 5
Catalyst is made according to comparative example 1, has carried out the stabilization of 100 h to catalyst according to the evaluation condition of embodiment 3
Property evaluation experimental, 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 |
2 stability test evaluation result of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 4 | 99.0 | 98.8 |
| Comparative example 5 | 86.1 | 85.0 |
By Tables 1 and 2 result as it can be seen that activity, selectivity and the stability of catalyst of the present invention are urged significantly better than comparative example
Agent.
Claims (18)
1. a kind of preparation method of heteropoly acid ammonium salt catalyst, the heteropoly acid ammonium salt catalyst include active component, auxiliary agent and
Carrier, active component are that ammonium heteropoly acids are shown in formula (1), and auxiliary agent is nickel oxide and di-iron trioxide, and carrier is amorphous silica-alumina packet
The silica covered；The weight of amorphous silica-alumina accounts for the 15% ~ 45% of vehicle weight；On the basis of the weight of catalyst, heteropoly acid ammonium
The content of salt is 8% ~ 30%, and for auxiliary agent in terms of oxide, the content of nickel oxide is 3% ~ 18%, the content of di-iron trioxide is 1% ~
10%, the content of carrier is 42% ~ 88%；
Hm(NH4)nYX12O40(1)
Wherein X represents W or Mo, and Y represents Si or P；When Y represents Si, m+n=4, n value is 0.1 ~ 1.0；When Y represents P, m
+ n=3, n value are 0.1 ~ 1.0；
The preparation method of the catalyst, comprising:
(1) carrier of amorphous silica-alumina cladding silica is prepared；
(2) auxiliary agent nickel and iron are loaded on the carrier of step (1) preparation, obtains catalyst precarsor A；
(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, then adjust Hydrogen Vapor Pressure to 2~4MPa, 100~
0.5~5.0h is reacted at 300 DEG C；
(5) the catalyst precarsor A after reaction in step (4) is filtered out, is dried at room temperature, until sample surfaces without
Liquid phase obtains catalyst precarsor B；
(6) the catalyst precarsor B that step (5) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated, and is obtained
Catalyst precarsor C；
(7) the catalyst precarsor C that step (6) obtains is added in the alkaline solution containing ammonium, through filtering, at 40 DEG C ~ 90 DEG C
It is dry；Or the catalyst precarsor C that step (6) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(8) aqueous solution of heteropoly acid being added in the catalyst precarsor D that step (7) obtains, heating stirring to solution is evaporated, then
Through dry and roasting to get catalyst.
2. preparation method described in accordance with the claim 1, it is characterised in that: in the carrier, the weight of amorphous silica-alumina accounts for load
The 16% ~ 40% of body weight.
3. preparation method described in accordance with the claim 1, it is characterised in that: on the basis of the weight of catalyst, ammonium heteropoly acids
Content be 12% ~ 25%, for auxiliary agent in terms of oxide, the content of nickel oxide is 5% ~ 15%, and the content of di-iron trioxide is 2% ~ 7%,
The content of carrier is 53% ~ 81%.
4. preparation method described in accordance with the claim 1, it is characterised in that: in the heteropoly acid ammonium salt catalyst, heteropoly acid
Ammonium salt is distributed in the outer surface of carrier.
5. preparation method described in accordance with the claim 1, it is characterised in that: in the amorphous silica-alumina, the quality of silica
Content is 15% ~ 50%.
6. preparation method described in accordance with the claim 1, it is characterised in that: in step (1), the amorphous silica-alumina coats oxygen
The carrier of SiClx the preparation method is as follows: first prepare silica support, then coated again with amorphous silica-alumina, the oxygen
The property of SiClx carrier is as follows: specific surface area is 500 ~ 820 m20.62 ~ 0.92 mL/g of/g, Kong Rongwei, average pore diameter are
4.6~6.6 nm。
7. preparation method according to claim 6, it is characterised in that: silica support is formed by silica rubber powder, done
Dry to obtain with roasting, the shape of silica support is using spherical, partial size 0.1 mm ~ 0.5 mm；The amorphous silica-alumina packet
The carrier for covering silica is prepared using rolling balling method, the method is as follows: silica support is put into bowling machine, in rolling process
In be equably sprinkled into amorphous silica-alumina dry powder and spray into binder, so that carrier is constantly grown up, the carrier after balling-up 30 DEG C ~
The dry h of 3 h ~ 24 at 50 DEG C, then in 400 DEG C ~ 700 DEG C roasting 2 h ~ 6 h；The binder is that mass concentration is 5 %
The dilute acid soln of ~ 10 %；The additional amount of binder and the mass ratio of amorphous silica-alumina dry powder are 0.5 ~ 1.5.
8. preparation method described in accordance with the claim 1, it is characterised in that: in step (2), auxiliary agent nickel and iron are loaded to carrier
On method use infusion process, it is after immersion, as follows using dry and roasting condition: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h,
Roasting condition is as follows: in 300 DEG C ~ 500 DEG C roasting 2 h ~ 6 h.
9. preparation method described in accordance with the claim 1, it is characterised in that: in step (3), the reduction treatment process is such as
Under: catalyst precarsor is warming up to 300 DEG C~600 DEG C under hydrogen atmosphere, 4h~8h is handled at 0.1MPa~0.5MPa.
10. preparation method described in accordance with the claim 1, it is characterised in that: in step (4), the polyalcohol is C5~C10
One of polyalcohol is a variety of；The mass concentration of polyalcohol and/or furfuryl aldehyde solution is 5%~35%, polyalcohol and/or furfural
The mass ratio of additional amount and step (1) resulting catalyst carrier is 2:1 ~ 10:1.
11. preparation method according to claim 10, it is characterised in that: in step (4), polyalcohol and/or furfuryl aldehyde solution
Mass concentration be 5%~30%, the additional amount of polyalcohol and/or furfural and the mass ratio of step (1) resulting catalyst carrier
For 3:1 ~ 10:1.
12. preparation method described in accordance with the claim 1, it is characterised in that: in step (6), the organic acid is citric acid, wine
One of stone acid, malic acid are a variety of, and the mass ratio of the organic acid and carrier is 0.1 ~ 0.4.
13. preparation method described in accordance with the claim 1, it is characterised in that: in step (7), catalyst that step (6) is obtained
Precursor C, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is the min of 5 min ~ 30；It is urged what step (6) obtained
Agent precursor C adsorbs ammonia, and adsorption time is the min of 5 min ~ 30；In step (7), the alkaline solution containing ammonium is ammonia
One of water, sal volatile, ammonium bicarbonate soln are a variety of.
14. preparation method described in accordance with the claim 1, it is characterised in that: in step (8), the heteropoly acid be phosphotungstic acid,
One of silico-tungstic acid, phosphomolybdic acid are a variety of.
15. preparation method described in accordance with the claim 1, it is characterised in that: dry and roasting condition described in step (8) is such as
Under: in 90 DEG C ~ 120 DEG C drying h of 3 h ~ 12, in 300 DEG C ~ 550 DEG C roasting 2 h ~ 6 h.
16. a kind of heteropoly acid ammonium salt catalyst, it is characterised in that: using any preparation method system of claim 1-15
?.
17. a kind of method of producing ethylene by ethanol dehydration, it is characterised in that using the catalyst described in claim 16.
18. according to the method for claim 17, it is characterised in that: the method for producing ethylene by ethanol dehydration uses fixed bed work
The reaction condition of skill, the preparing ethylene by dehydrating ethanol is as follows: ethanol water concentration is 5wt% ~ 40wt%, mass space velocity
0.5 h-1~15.0 h-1, 160 DEG C ~ 400 DEG C of reaction temperature.
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