CN106944146B - A kind of preparation method of heteropoly acid ammonium catalyst - Google Patents
A kind of preparation method of heteropoly acid ammonium catalyst Download PDFInfo
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- CN106944146B CN106944146B CN201610003166.8A CN201610003166A CN106944146B CN 106944146 B CN106944146 B CN 106944146B CN 201610003166 A CN201610003166 A CN 201610003166A CN 106944146 B CN106944146 B CN 106944146B
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- catalyst
- acid
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- ammonium
- catalyst precarsor
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- 150000007513 acids Chemical class 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 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
- 230000009467 reduction Effects 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 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 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 13
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- 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 12
- 238000001914 filtration Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 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 4
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical group Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-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
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 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 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 235000005985 organic acids Nutrition 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
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims 1
- 229940038384 octadecane Drugs 0.000 claims 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 66
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 25
- 239000005977 Ethylene Substances 0.000 abstract description 25
- 230000018044 dehydration Effects 0.000 abstract description 7
- 238000006297 dehydration reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000004939 coking Methods 0.000 abstract 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 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
- 239000000047 product Substances 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 229910020628 SiW12O40 Inorganic materials 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
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005336 cracking 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- KVIPHDKUOLVVQN-UHFFFAOYSA-N ethene;hydrate Chemical group O.C=C KVIPHDKUOLVVQN-UHFFFAOYSA-N 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
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000069 nitrogen hydride 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
- 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
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
-
- 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
Abstract
The invention discloses a kind of preparation methods of heteropoly acid ammonium catalyst.The catalyst includes active component, auxiliary agent and carrier component, and active component is ammonium heteropoly acids, and auxiliary agent is nickel oxide, and carrier component is silica, and preparation method is to prepare the catalyst precarsor A containing heteropoly acid and auxiliary agent nickel；Catalyst precarsor A is after reduction treatment and furfurol reaction processing, then successively loads organic acid, ammoniumization processing, leaching heteropoly acid solution and obtain catalyst through dry and roasting.The catalyst that the method for the present invention obtains is ethylene reaction produced especially suitable for the dehydration that low-concentration ethanol aqueous solution is raw material, while low temperature active with higher, selectivity and coking resistivity, improves the stability of catalyst.
Description
Technical field
The invention discloses a kind of preparation methods of heteropoly acid ammonium catalyst, raw for ethanol dehydration more particularly to one kind
Produce the preparation method of the heteropoly acid ammonium salt catalyst 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.
Li Benxiang etc. [Chemical Engineering Technology and exploitation, 2010,5 (39): 7-9] reports the entitled load of MCM- 41 silico-tungstic acid and urges
Change the article of producing ethylene from dehydration of ethanol, catalyst is prepared using infusion process.It is de- that CN200910057539.X discloses a kind of ethyl alcohol
The catalyst of water ethylene.For the catalyst using aluminium oxide as carrier, active component is heteropoly acid, is prepared using kneading method.It is above-mentioned
Catalyst shows higher catalytic activity and selectivity when using high concentration ethanol as raw material, but works as with low-concentration ethanol and be
When raw 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 preparation methods of heteropoly acid ammonium catalyst.It should
The resulting catalyst of method not only has the characteristics that low temperature active is high, selectivity is good, has strong anti-carbon capacity, and stability is good.
The preparation method of the heteropoly acid ammonium catalyst, comprising:
(1) the catalyst precarsor A containing ammonium heteropoly acids, auxiliary agent nickel and carrier component silica is prepared；
(2) the catalyst precarsor A of step (1) is added in autoclave, reduction treatment is carried out to it using hydrogen；
(3) furfuryl aldehyde solution is added in autoclave, then adjusts Hydrogen Vapor Pressure to 2~4MPa, at 100 DEG C~300 DEG C
Lower reaction 0.5h~5.0h；
(4) material filtering after reaction in step (3) is come out, low temperature drying to sample surfaces is catalyzed without liquid phase
Agent precursor B；
(5) the catalyst precarsor B that step (4) obtains being added in aqueous solutions of organic acids, heating stirring to solution is evaporated,
Obtain catalyst precarsor C；
(6) the catalyst precarsor C that step (5) 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 (5) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(7) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (6) obtains, heating stirring to solution is steamed
It is dry；
(8) solid for obtaining step (7) is through dry and roasting to get catalyst.
The heteropoly acid ammonium catalyst that the method for the present invention obtains, including active component, auxiliary agent and carrier component, active component be
Ammonium heteropoly acids are shown in formula (1) that auxiliary agent is nickel oxide, and carrier component is silica；On the basis of the weight of catalyst, heteropoly acid ammonium
The content of salt is 5% ~ 45%, preferably 15% ~ 40%, further preferably 20% ~ 40%, and in terms of oxide, nickel oxide contains auxiliary agent
Amount is 3% ~ 15%, and the content of silica is 40% ~ 92%, preferably 45% ~ 82%；
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 method for the present invention, the property of the catalyst precarsor A of step (1) is as follows: specific surface area is 400 ~ 750 m2/ g, hole
Holding is 0.50 ~ 0.80 mL/g, and average pore diameter is 4.1 ~ 6.2 nm.
In the method for the present invention, the preparation method of step (1) catalyst precarsor A is preferably as follows:
A, template is added in the aqueous solution containing organic acid, obtains solution I；
B, silicon source is added in solution I, obtains solution II, then stirred at 60 DEG C ~ 90 DEG C at gel；
C, by gel at 20 DEG C ~ 50 DEG C aging 8h ~ for 24 hours, then in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 300
DEG C ~ 550 DEG C of roasting 2.0h ~ 6.0h, catalyst precarsor A is made；
Wherein heteropoly acid and auxiliary agent nickel can be introduced into carrier using conventional method, can be in step A, step B, step C
In introduce in any step or a few steps, heteropoly acid and auxiliary agent nickel can introduce simultaneously, can also introduce respectively, such as infusion process, mixed
Legal, total glue method etc..It introduces adoptable presoma when auxiliary agent nickel and is selected from one of nickel nitrate, nickel acetate or a variety of.
In the method for the present invention, it may be incorporated into other adjuvant components, such as boron in catalyst precarsor A, in terms of oxide,
Weight content in catalyst is 6% or less.
In the method for the present invention, it may be incorporated into other adjuvant components, such as iron in catalyst precarsor A, with di-iron trioxide
Meter, weight content in the catalyst are 10% or less.
In the method for the present invention, other adjuvant components can be introduced into catalyst precarsor A using conventional method, can be in step
A, other adjuvant components, such as infusion process, mixing method, altogether glue method etc. are introduced in any step or a few steps in step B, step C.
Step A, the template are dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, hexadecane
Base trimethylammonium bromide, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorination
One of ammonium, hexamethylenetetramine are a variety of, and the template and step B silicon source are with SiO2The molar ratio of meter be 0.01 ~
1.2。
Organic acid is one of citric acid, tartaric acid, malic acid or a variety of, the organic acid and step B in step A
Silicon source is with SiO2The molar ratio of meter is 0.1 ~ 1.2.
In step B, the silicon source is one of ethyl orthosilicate, silica solution or a variety of.
Molding catalyst precarsor can be made in the catalyst precarsor A, be also possible to before being not required to molding catalyst
Body, those skilled in the art determine according to selected technique.Molding catalyst precarsor, can using existing routine at
Type technology forms, such as extruded moulding, compression molding etc., and shape can be bar shaped, spherical shape, sheet etc..In forming process,
It can according to need addition binder and shaping assistant, binder generally use small porous aluminum oxide.Shaping assistant such as peptizing agent,
Extrusion aid etc..
In step (1) and step (7), the heteropoly acid is one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
The molar ratio that heteropoly acid is introduced in step (1) and step (7) is 4:1 ~ 1:4.
In step (2), 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 (3), the mass concentration of the furfuryl aldehyde solution is 5%~35%, preferably 5%~30%, the addition of furfural
The mass ratio of amount and step (1) resulting catalyst precarsor A are 2:1 ~ 10:1, preferably 3:1 ~ 10:1.
In step (4), low temperature drying can carry out at room temperature.
In step (5), the organic acid is one of citric acid, tartaric acid, malic acid or a variety of.The organic acid
With SiO in catalyst precarsor A2Molar ratio be 0.05 ~ 0.50.
In step (6), the solid that step (5) obtains is added in the alkaline solution containing ammonia and is impregnated, dip time
Generally 5min ~ 30min；The solid absorption ammonia that step (5) is obtained, adsorption time are generally 5min ~ 30min.Step (6)
In, the alkaline solution containing ammonium is one of ammonium hydroxide, sal volatile, ammonium bicarbonate soln or a variety of.
In step (7), the ammonia is using pure ammonia or uses the gaseous mixture containing ammonia, removes ammonia in mixed gas
Outside, other is one of inert nitrogen gas, argon gas or a variety of.
The temperature of heating stirring is generally 40~90 DEG C in step (5) or step (7).
Drying described in step (8) and roasting condition are as follows: in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 300 DEG C ~
550 DEG C of roasting 2h ~ 6h.
The catalyst of the method for the present invention preparation is anti-especially suitable for the dehydration ethylene that low-concentration ethanol aqueous solution is raw material
It answers.The reaction condition of 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, 180 DEG C ~ 400 DEG C of reaction temperature.
Catalyst of the present invention uses the silica support of bigger serface, using the hydrogenation of auxiliary agent nickel, in autoclave
Interior catalysis furfural liquid-phase hydrogenatin mainly has two aspect effects: one is the liquid alkane that furfural liquid-phase hydrogenatin generates is adsorbed on and urges
On agent carrier, the duct of carrier can be effectively blocked, is distributed the heteropoly acid ammonium of subsequent load on the surface of the carrier, in this way
Major part ammonium heteropoly acids are made to be dispersed in carrier surface, smaller portions ammonium heteropoly acids are dispersed in carrier duct；Another party
Face, furfural liquid-phase hydrogenatin can generate carbon distribution on carrier, can weaken the acidity of carrier to a certain extent, reduce support acidity
The quantity of position absorption ammonia, makes heteropoly acid mainly react with ammonium salt organic acid and generates ammonium heteropoly acids, facilitate heteropoly acid ammonium
Salt is evenly dispersed in carrier surface, and can remove above-mentioned carbon deposit through subsequent high-temperature roasting, effectively remains this portion in this way
Fractional bearer acidic site.The catalyst that the method for the present invention obtains not only has that low temperature active is high, selectivity is good, has strong anti-carbon capacity
Feature, 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 catalyst:
31.1g nickel nitrate, 8.6g phosphotungstic acid, 97.5g cetyl trimethylammonium bromide and 137.0g citric acid is weighed to match
At mixed solution, 202.3mL tetraethyl orthosilicate is added in mixed solution, stir 2 h, then at 70 DEG C stirring at
Gel, by gel, 12 h of aging, dry 8 h at 110 DEG C, compression molding are made then in 450 DEG C of 3 h of roasting at 40 DEG C
Catalyst precarsor A is obtained, is then added in autoclave, 450 DEG C is warming up under hydrogen atmosphere, handle 4h at 0.3MPa,
It is down to reaction temperature, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusts Hydrogen Vapor Pressure to 3MPa, at 150 DEG C
Reaction 3h after reaction comes out catalyst filtration, dries to carrier surface at 40 DEG C without liquid phase, is then added to and contains
In the aqueous solution for having 32.2g citric acid, stirring to solution is evaporated at 40 DEG C；Obtained material, which is added in sal volatile, to be soaked
Stain 10min is dry at 40 DEG C after filtering；It is added in the aqueous solution containing 17.3g phosphotungstic acid, stirs at 40 DEG C to solution
It 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, (NH is made4)0.2H2.8PW12O40-
NiO/SiO2Catalyst, wherein NiO content is 10wt%, (NH4)0.2H2.8PW12O40Content is 25wt%.Wherein cetyl front three
The molar ratio of base ammonium bromide and silica is 0.3, and the molar ratio of citric acid and silica is 0.8.The property of catalyst precarsor A is such as
Under: specific surface area is 450 m20.56 mL/g of/g, Kong Rongwei, average pore diameter are 5.0 nm.(2) evaluation of catalyst:
Evaluating catalyst carries out in atmospheric fixed bed tubular reactor, and raw material is 20wt% ethanol water, mass space velocity
7 h-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
38.9g nickel nitrate, 14.5g phosphotungstic acid, 168.4g cetyl trimethylammonium bromide and 88.8g citric acid is weighed to match
At mixed solution, 210.4mL tetraethyl orthosilicate is added in mixed solution, stir 2 h, then at 70 DEG C stirring at
Gel, by gel, 12 h of aging, dry 8 h at 110 DEG C, compression molding are made then in 450 DEG C of 3 h of roasting at 40 DEG C
Catalyst precarsor A is obtained, is then added in autoclave, 450 DEG C is warming up under hydrogen atmosphere, handle 4h at 0.3MPa,
It is down to reaction temperature, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusts Hydrogen Vapor Pressure to 3MPa, at 160 DEG C
Reaction 2h after reaction comes out catalyst filtration, dries to carrier surface at 40 DEG C without liquid phase；It is then added to and contains
In the aqueous solution for having 48.8g citric acid, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, to be soaked
Stain 10min is dry at 60 DEG C after filtering；Be then added in the aqueous solution containing 14.5g phosphotungstic acid, stirred at 70 DEG C to
Solution is evaporated, and by obtained solid in 110 DEG C of dry 8.0 h, then in 500 DEG C of 3.0 h of roasting, (NH is made4)0.5H2.5PW12O40-NiO/SiO2Catalyst, wherein NiO content is 11wt%, (NH4)0.5H2.5PW12O40Content is 28wt%.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.Catalyst
The property of precursor A is as follows: specific surface area is 480 m20.61 mL/g of/g, Kong Rongwei, average pore diameter are 5.0 nm.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 3
46.7g nickel nitrate, 20.7g phosphotungstic acid, 271g cetyl trimethylammonium bromide and 53.5g citric acid is weighed to be made into
211mL tetraethyl orthosilicate is added in mixed solution by mixed solution, stirs 2 h, is then stirred at 70 DEG C to Cheng Ning
Glue, by gel, 12 h of aging, dry 8 h at 110 DEG C, compression molding are made then in 450 DEG C of 3 h of roasting at 40 DEG C
Catalyst precarsor A, is then added in autoclave, and 450 DEG C are warming up under hydrogen atmosphere, and 4h is handled at 0.3MPa, drop
To reaction temperature, the furfuryl aldehyde solution that 400g mass concentration is 20% is added, then adjusting Hydrogen Vapor Pressure to 3MPa, it is anti-at 150 DEG C
It answers 3h, after reaction, catalyst filtration is come out, dries to carrier surface at 40 DEG C without liquid phase；Be then added to containing
In the aqueous solution of 65.0g citric acid, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, to be impregnated
10min is dry at 60 DEG C after filtering；It is then added in the aqueous solution containing 10.4g phosphotungstic acid, stirs at 70 DEG C to molten
Liquid is evaporated, and by obtained solid in 110 DEG C of dry 8.0 h, then in 470 DEG C of 3.0 h of roasting, (NH is made4)0.7H2.3PW12O40-
NiO/SiO2Catalyst, wherein NiO content is 12wt%, (NH4)0.7H2.3PW12O40Content is 30wt%.Wherein cetyl front three
The molar ratio of base ammonium bromide and silica is 0.8, and the molar ratio of citric acid and silica is 0.3.The property of catalyst precarsor A is such as
Under: specific surface area is 460 m20.60 mL/g of/g, Kong Rongwei, average pore diameter are 5.2 nm.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 4
In embodiment 3, cetyl trimethylammonium bromide is changed to 303.5g Cetyltrimethylammonium bromide,
Remaining same embodiment 3, gained catalyst are (NH4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%,
(NH4)0.7H2.3PW12O40Content is 30wt%, Cetyltrimethylammonium bromide and SiO2Molar ratio be 0.8.Catalyst precarsor
The property of A is as follows: specific surface area is 450 m20.62 mL/g of/g, Kong Rongwei, average pore diameter are 5.2 nm.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 5
In embodiment 3, phosphotungstic acid is changed to silico-tungstic acid, cetyl trimethylammonium bromide is changed to 238.4g dodecane
Base trimethylammonium bromide impregnates 10min in sal volatile and is changed to absorption 10v% NH3/ Ar gaseous mixture 10min, remaining is the same as real
Example 3 is applied, catalyst (NH is made4)0.7H3.3SiW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%, (NH4)0.7H3.3SiW12O40Content is 30wt%, dodecyl trimethyl ammonium bromide and SiO2Molar ratio be 0.8.Catalyst precarsor A's
Property is as follows: specific surface area is 485 m20.59 mL/g of/g, Kong Rongwei, average pore diameter are 4.9 nm.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Embodiment 6
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
It weighs 271g cetyl trimethylammonium bromide and 53.5g citric acid is made into mixed solution, by the positive silicic acid four of 211mL
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,
Dry 8 h, compression molding obtain catalyst carrier then in 450 DEG C of 3 h of roasting at 110 DEG C.Carrier is directly added into
Into the mixed aqueous solution containing 46.7g nickel nitrate and 31.1g phosphotungstic acid, stirring to solution is evaporated at 70 DEG C；By what is obtained
In 110 DEG C of dry 8.0 h, then in 350 DEG C of 3.0 h of roasting, H is made in solid3PW12O40-NiO/SiO2Catalyst, wherein NiO
Content is 12wt%, H3PW12O40Content is 30wt%.Catalyst property is listed in table 1.The property of catalyst carrier is as follows: specific surface
Product is 450 m20.58 mL/g of/g, Kong Rongwei, average pore diameter are 5.1 nm.The evaluation of catalyst turns with embodiment 1, ethyl alcohol
Rate and ethylene selectivity the results are shown in Table 1.
Comparative example 2
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 65.0g citric acid, stirs at 70 DEG C to solution
It is evaporated；Obtained material, which is added in sal volatile, impregnates 10min, dry at 60 DEG C after filtering；Be then added to containing
In the aqueous solution of 10.4g 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 470 DEG C of 3.0 h of roasting, (NH is made4)0.7H2.3PW12O40-NiO/SiO2Catalyst, wherein NiO content is 12wt%,
(NH4)0.7H2.3PW12O40Content is 30wt%.Wherein the molar ratio of cetyl trimethylammonium bromide and silica is 0.8, lemon
The molar ratio of acid and silica is 0.3.
The evaluation of catalyst the results are shown in Table 1 with embodiment 1, ethanol conversion and ethylene selectivity.
Comparative example 3
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 | 99.5 | 98.9 |
| Embodiment 2 | 99.3 | 98.8 |
| Embodiment 3 | 99.3 | 99.0 |
| Embodiment 4 | 99.4 | 99.1 |
| Embodiment 5 | 99.1 | 98.7 |
| Comparative example 1 | 96.5 | 95.3 |
| Comparative example 2 | 96.9 | 96.5 |
2 stability test evaluation result of table
| Conversion ratio, wt% | Selectivity, wt% | |
| Embodiment 6 | 98.8 | 98.6 |
| Comparative example 3 | 83.1 | 82.1 |
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 (17)
1. a kind of preparation method of heteropoly acid ammonium catalyst, comprising:
(1) the catalyst precarsor A containing ammonium heteropoly acids, auxiliary agent nickel and carrier component silica is prepared；
(2) the catalyst precarsor A of step (1) is added in autoclave, reduction treatment is carried out to it using hydrogen；
(3) furfuryl aldehyde solution is added in autoclave, then adjusting Hydrogen Vapor Pressure to 2~4MPa, it is anti-at 100 DEG C~300 DEG C
Answer 0.5h~5.0h；
(4) material filtering after reaction in step (3) is come out, low temperature drying to sample surfaces is without liquid phase, before obtaining catalyst
Body B；
(5) the catalyst precarsor B that step (4) obtains is added in aqueous solutions of organic acids, heating stirring to solution is evaporated, and is obtained
Catalyst precarsor C；
(6) the catalyst precarsor C that step (5) 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 (5) obtains is adsorbed into ammonia at 40 DEG C ~ 90 DEG C, obtain catalyst precarsor D；
(7) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (6) obtains, heating stirring to solution is evaporated；
(8) solid for obtaining step (7) is through dry and roasting to get catalyst.
2. preparation method described in accordance with the claim 1, it is characterised in that: the heteropoly acid ammonium catalyst, including active component, help
Agent and carrier component, active component are that ammonium heteropoly acids are shown in formula (1) that auxiliary agent is nickel oxide, and carrier component is silica；With catalysis
On the basis of the weight of agent, the content of ammonium heteropoly acids is 5% ~ 45%, and for auxiliary agent in terms of oxide, the content of nickel oxide is 3% ~ 15%,
The content of silica is 40% ~ 92%；
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.
3. preparation method according to claim 2, it is characterised in that: on the basis of the weight of catalyst, ammonium heteropoly acids contain
Amount is 15% ~ 40%, and for auxiliary agent in terms of oxide, the content of nickel oxide is 3% ~ 15%, and the content of silica is 45% ~ 82%.
4. preparation method according to claim 1 or 2, it is characterised in that: contain boron in catalyst precarsor A, in terms of oxide,
Weight content in catalyst is 6% or less.
5. preparation method according to claim 1 or 2, it is characterised in that: contain iron in catalyst precarsor A, with di-iron trioxide
Meter, weight content in the catalyst are 10% or less.
6. preparation method described in accordance with the claim 1, it is characterised in that the property of catalyst precarsor A described in step (1) is as follows: ratio
Surface area is 400 ~ 750 m20.50 ~ 0.80 mL/g of/g, Kong Rongwei, average pore diameter are 4.1 ~ 6.2 nm.
7. according to preparation method described in claim 1 or 6, it is characterised in that the preparation method of catalyst precarsor A described in step (1)
It is as follows:
A, template is added in the aqueous solution containing organic acid, obtains solution I；
B, silicon source is added in solution I, obtains solution II, then stirred at 60 DEG C ~ 90 DEG C at gel；
C, by gel at 20 DEG C ~ 50 DEG C aging 8h ~ for 24 hours, then in 90 DEG C ~ 120 DEG C dry 3h ~ 12h, then 300 DEG C ~
550 DEG C of roasting 2.0h ~ 6.0h, are made catalyst precarsor A；
Wherein heteropoly acid and auxiliary agent nickel introduce in any step or a few steps in step A, step B, step C.
8. preparation method according to claim 7, it is characterised in that: in step A, the template is trimethyl
Ammonium bromide, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, octadecane
One of base trimethylammonium bromide, octadecyltrimethylammonium chloride, hexamethylenetetramine are a variety of, the template with
Step B silicon source is with SiO2The molar ratio of meter is 0.01 ~ 1.2.
9. preparation method according to claim 7, it is characterised in that: organic acid is citric acid, tartaric acid, malic acid in step A
One of or it is a variety of, the organic acid and step B silicon source are with SiO2The molar ratio of meter is 0.1 ~ 1.2.
10. preparation method according to claim 7, it is characterised in that: in step B, the silicon source is ethyl orthosilicate, silicon is molten
One of glue is a variety of.
11. preparation method described in accordance with the claim 1, it is characterised in that: miscellaneous more in the ammonium heteropoly acids in step (1)
Acid source is in one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of；In step (7), the heteropoly acid is phosphotungstic acid, silicon tungsten
One of acid, phosphomolybdic acid are a variety of；Step (1) be introduced into ammonium heteropoly acids in terms of heteropoly acid with step (7) in introduce heteropoly acid
Molar ratio be 4:1 ~ 1:4.
12. preparation method described in accordance with the claim 1, it is characterised in that: in step (2), the reduction treatment process is as follows: hydrogen
Catalyst precarsor is warming up to 300 DEG C~600 DEG C under gas atmosphere, 4h~8h is handled at 0.1MPa~0.5MPa.
13. preparation method described in accordance with the claim 1, it is characterised in that: in step (3), the mass concentration of the furfuryl aldehyde solution
It is 5%~35%, the additional amount of furfural and the mass ratio of step (1) resulting catalyst precarsor A are 2:1 ~ 10:1.
14. preparation method described in accordance with the claim 1, it is characterised in that: in step (3), the mass concentration of the furfuryl aldehyde solution
It is 5%~30%, the additional amount of furfural and the mass ratio of step (1) resulting catalyst precarsor A are 3:1 ~ 10:1.
15. preparation method described in accordance with the claim 1, it is characterised in that: in step (5), the organic acid is citric acid, winestone
One of acid, malic acid are a variety of；SiO in the organic acid and catalyst precarsor A2Molar ratio be 0.05 ~ 0.50.
16. preparation method described in accordance with the claim 1, it is characterised in that: in step (6), catalyst precarsor that step (5) is obtained
C, which is added in the alkaline solution containing ammonium, to be impregnated, and dip time is 5min ~ 30min；Before the catalyst that step (5) is obtained
Body C adsorbs ammonia, and adsorption time is 5min ~ 30min；In step (6), the alkaline solution containing ammonium is ammonium hydroxide, ammonium carbonate
One of solution, ammonium bicarbonate soln are a variety of.
17. preparation method described in accordance with the claim 1, it is characterised in that: drying described in step (8) and roasting condition are as follows:
90 DEG C ~ 120 DEG C dry 3h ~ 12h, then in 300 DEG C ~ 550 DEG C roasting 2h ~ 6h.
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