CN107297224B - A kind of hydrocracking catalyst and preparation method thereof - Google Patents
A kind of hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN107297224B CN107297224B CN201610239074.XA CN201610239074A CN107297224B CN 107297224 B CN107297224 B CN 107297224B CN 201610239074 A CN201610239074 A CN 201610239074A CN 107297224 B CN107297224 B CN 107297224B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 150000007513 acids Chemical class 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011964 heteropoly acid Substances 0.000 claims description 21
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- -1 molybdate compound Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 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
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 230000002198 cosolvency Effects 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 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
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 150000002816 nickel compounds Chemical class 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 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
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 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
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-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
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- 239000001099 ammonium carbonate Substances 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 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 1
- 239000004575 stone Substances 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000005336 cracking Methods 0.000 description 10
- 229910018104 Ni-P Inorganic materials 0.000 description 9
- 229910018536 Ni—P Inorganic materials 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 235000005979 Citrus limon Nutrition 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 244000248349 Citrus limon Species 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000008246 gaseous mixture 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
- 150000003222 pyridines Chemical class 0.000 description 2
- 239000002994 raw material 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
- 239000000126 substance Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229910020628 SiW12O40 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- 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
- B01J27/19—Molybdenum
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrocracking catalyst and preparation method thereof, the hydrocracking catalyst includes acidic components, hydrogenation metal component and carrier, and acidic components are ammonium heteropoly acids, and hydrogenation metal component is Mo and Ni, and P is auxiliary agent, and carrier is silica.A kind of preparation method of above-mentioned hydrocracking catalyst is also provided.The catalyst that the method for the present invention obtains shows higher reactivity and liquid hydrocarbon-selective in the hydrocracking reaction for long chain alkane.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, especially a kind of long alkane with high activity
Hydrocarbon hydrocracking catalyst and preparation method thereof.
Background technique
In petroleum refining industry, it is that feedstock oil exists that being hydrocracked, which is by the important process of mink cell focus production high-quality light-weight oil product,
High temperature, high pressure carry out adding hydrogen, desulfurization, denitrogenation, molecular skeleton rearrangement and cracking etc. chemical under the conditions of facing existing for hydrogen and catalyst
A kind of conversion process of reaction.Hydrocracking process can not only produce high grade light-end products, and liquid-phase product high income, skill
Art core is catalyst.Hydrocracking catalyst is a kind of bifunctional catalyst, has both acid function and hydrogenating function.US5,
536,687, the acid function of hydrocracking catalyst involved in US5,447,623 and EP0028938A1 is mainly by dividing
Son sieve provides, and hydrogenation component selects Mo-Ni or W-Ni.Catalyst zeolite containing Y 20%~40% involved by CN1389545A,
Phosphorus heteropoly tungstic acid or silicotungstic heteropolyacid 5%~20%, nickel oxide 5%~10%, aluminium oxide 40%~60%.Above-mentioned is adding containing molecular sieve
Hydrogen Cracking catalyst has acid strong, a big advantage of specific surface, but the disadvantage is that molecular sieve bore diameter is small, so as to cause reactant with
Product diffusional resistance increases, and the probability of second pyrolysis reaction increases.
CN1927461A discloses a kind of hydrocracking catalyst containing heteropoly acid, and heteropoly acid can be phosphotungstic acid or silicon tungsten
Acid, content are 40%~60%, and hydrogenation component (in terms of simple substance) preferably 5%~10%, surplus is carrier.Nothing is selected when preparation according to the ratio
Machine heat proof material particulate vector prepares the aqueous metal salt of hydrogenation component, impregnated carrier as catalyst carrier；Liquid is consolidated point
Solids drying from after, roasting；Heteropoly acid aqueous solution is prepared, solids obtained is impregnated, stands, dry, roasting.This contains miscellaneous
The hydrocracking catalyst of polyacid have the advantages that it is acid by force and aperture is big, but the disadvantage is that phosphotungstic acid high water solubility, use
A possibility that being relatively easy to run off in the process, and since the catalyst has highly acid, increasing second pyrolysis reaction.
CN201110350796.X discloses hydrocracking catalyst and preparation method thereof.The catalyst includes acid group
Point, hydrogenation component and carrier, acidic components are heteropoly acid alkali metal salt, and hydrogenation component is nickel, and carrier is silica；Catalyst is each
Content is acidic components 10%~20% to component by mass percentage, and hydrogenation component 3%~8%, surplus is carrier.This method is
Catalyst carrier is prepared using sol-gal process, and introduces hydrogenation metal component and alkali metal salt in carrier preparation process, it will
Carrier immerses heteropoly acid solution, up to catalyst after drying.The invention catalyst, heteropolyacid salt is evenly dispersed in the carrier, by
Acid weaker in it, content is lower, shows high liquid hydrocarbon-selective, but activity is relatively low.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of hydrocracking catalysts with high activity
And preparation method thereof.
The present invention provides a kind of hydrocracking catalyst, and the hydrocracking catalyst includes acidic components, hydrogenation metal
Component and carrier, acidic components are ammonium heteropoly acids, and hydrogenation metal component is Mo and Ni, and P is auxiliary agent, and carrier is silica；With
On the basis of the weight of catalyst, the content of acidic components is 30%~40%, MoO3The content that content is 5%~15%, NiO is 1%~
5%, P content is 0.5%~3%, and surplus is silica support；The property of the hydrocracking catalyst is as follows: specific surface area is
300~450 m20.40~0.55mL/g of/g, Kong Rongwei, average pore diameter are 4.5~6.3nm, and ammonium heteropoly acids, which are distributed in, urges
Agent center is 1.6wt%~4.7wt% of total content to the content in 1/4 radius, is distributed in 1/4 radius to 1/2 radius
Content in range is 4.7wt%~14.1wt% of total content, be distributed in 1/2 radius to the content in 3/4 radius be total
7.8wt%~23.4wt% of content, the content being distributed within the scope of 3/4 radius to catalyst external surface are total content
57.8wt%~85.9wt%.
In hydrocracking catalyst of the present invention, the heteropolyacid salt molecular formula is Hm(NH4)nYX12O40, wherein X generation
Table W or Mo, Y represent 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 is
0.1~1.0.
The present invention provides a kind of preparation method of above-mentioned hydrocracking catalyst, the preparation side of the hydrocracking catalyst
Method includes the following steps:
(1) the cosolvency water of nickeliferous, molybdenum, phosphorus simultaneously is prepared with molybdate compound, nickel compound containing, phosphorus-containing compound and water
Solution；
(2) cosolvency aqueous solution, heteropoly acid and the template of nickeliferous, molybdenum, phosphorus that step (1) obtains are added to containing organic
In the aqueous solution of acid, mixed solution is obtained；
(3) silicon source is added in the solution that step (2) obtains and is uniformly mixed, then stirred at 40~90 DEG C to Cheng Ning
Glue, 8.0~24.0h of aging at 30~50 DEG C；
(4) it by step (3) resulting material in 90~120 DEG C of dry 3.0~12.0h, is then roasted at 300~550 DEG C
2.0~6.0h obtains catalyst precarsor A；
(5) the catalyst precarsor A that step (4) obtains is added in autoclave, it is carried out in a hydrogen atmosphere
Reduction treatment；
(6) long chain alkane solution is driven into autoclave described in step (5), then adjust Hydrogen Vapor Pressure to normal pressure~
1MPa reacts 3.0~8.0h at 350~450 DEG C；
(7) the catalyst precarsor A after reaction in step (6) is filtered out, is dried at 30 DEG C~40 DEG C, until
Sample surfaces obtain catalyst precarsor B without liquid phase；
(8) the catalyst precarsor B that step (7) obtains is added in aqueous solutions of organic acids, stirred at 40~90 DEG C to
Solution is evaporated, and obtains catalyst precarsor C；
(9) the catalyst precarsor C that step (8) obtains is added in the alkaline solution containing ammonium, through filtering, at 40~90 DEG C
Lower drying；Or the catalyst precarsor C that step (8) obtains is adsorbed into ammonia at 40~90 DEG C, obtain catalyst precarsor D；
(10) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (9) obtains, is stirred at 40~90 DEG C
It is evaporated to solution；
(11) then the solid for obtaining step (10) is roasted at 90~120 DEG C of dry 3.0~12.0h at 300~550 DEG C
2.0~6.0h is burnt to get catalyst.
In preparation method of the present invention, the heteropolyacid salt molecular formula is Hm(NH4)nYX12O40, wherein X represents W or Mo, Y
Represent 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 is 0.1~1.0.
In preparation method of the present invention, molybdate compound described in step (1) can be molybdenum oxide；The nickel compound containing can
Think that basic nickel carbonate, phosphorus-containing compound can be phosphoric acid.
In preparation method of the present invention, in step (1), nickeliferous, molybdenum, phosphorus the preparation of cosolvency aqueous solution can be by this field
Common method is prepared, and wherein Mo(is with MoO3Meter) concentration be 0.03~0.2 g/mL, Ni(is in terms of NiO) concentration be
The concentration of 0.005~0.08 g/mL, P are 0.002~0.03 g/mL.
In preparation method of the present invention, template described in step (2) is dodecyl trimethyl ammonium bromide, dodecyl
Trimethyl ammonium chloride, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide,
One of octadecyltrimethylammonium chloride, hexamethylenetetramine are a variety of, the template and step (3) silicon source with
SiO2The molar ratio of meter is 0.01~1.2.
In preparation method of the present invention, heteropoly acid described in step (2) and step (10) is phosphotungstic acid, silico-tungstic acid, phosphorus molybdenum
One of acid is a variety of.The molar ratio that heteropoly acid is introduced in step (2) and step (10) is 3:1~1:3.
In preparation method of the present invention, in step (2) organic acid be one of citric acid, tartaric acid, malic acid or a variety of,
The organic acid and step (3) silicon source is with SiO2The molar ratio of meter is 0.1~1.2.
In preparation method of the present invention, silicon source described in step (3) is ethyl orthosilicate and/or silica solution.
In preparation method of the present invention, molding catalyst precarsor can be made in catalyst precarsor A described in step (4),
It can be and be not required to molding catalyst precarsor, those skilled in the art determine according to selected technique.Molding catalyst
Precursor can be formed using existing conventional molding techniques, such as extruded moulding, compression molding etc., shape can for bar shaped,
Spherical shape, sheet etc..In forming process, it can according to need addition binder and shaping assistant, binder generally use aperture
Aluminium oxide.Shaping assistant such as peptizing agent, extrusion aid etc..After step (4), can be through molding or without molding, then pass through
High-temperature roasting obtains silica support, wherein the condition roasted is as follows: 300 DEG C~550 DEG C roasting 2.0 h~6.0 h.
In preparation method of the present invention, reduction treatment process described in step (5) is as follows: will be before catalyst under hydrogen atmosphere
Body is warming up to 300~600 DEG C, and 4.0~8.0h is handled at 0.1~0.5MPa.The hydrogen atmosphere that wherein reduction treatment uses can
To be pure hydrogen, it is also possible to the hydrogen containing inert gas, hydrogen volume concentration is 30%~100%.
In preparation method of the present invention, long chain alkane described in step (6) be one of C10~C16 long chain alkane or
It is a variety of, preferably one of n-decane, dodecane, hexadecane or a variety of；The additional amount of long chain alkane and the matter of catalyst precarsor A
Amount is than being 5:1~15:1.
In preparation method of the present invention, organic acid described in step (8) be one of citric acid, tartaric acid, malic acid or
It is a variety of.SiO in the organic acid and catalyst precarsor B2Molar ratio be 0.05~0.50.
In preparation method of the present invention, in step (9), the catalyst precarsor C that step (8) obtains is added to the alkalinity containing ammonia
It is impregnated in solution, dip time is 5~30min；The catalyst precarsor C that step (8) is obtained adsorbs ammonia, adsorption time
For 5~30 min.
In preparation method of the present invention, the alkaline solution containing ammonium described in step (9) is ammonium hydroxide, sal volatile, carbonic acid
One of hydrogen ammonium salt solution is a variety of.
In preparation method of the present invention, ammonia described in step (9) is using pure ammonia or uses the gaseous mixture containing ammonia
Body, in mixed gas in addition to ammonia, other is one of inert gas, nitrogen or a variety of.
Catalyst of the present invention utilizes the hydrogenation of metal, and long chain alkane is catalyzed in autoclave and is hydrocracked instead
It answers, mainly there is two aspect effects: one is the liquid alkane absorption that long chain alkane hydrogenation reaction generates is on a catalyst support, energy
Enough ducts for effectively blocking carrier are distributed the ammonium heteropoly acids of subsequent load on the surface of the carrier, make major part in this way
Ammonium heteropoly acids are dispersed in carrier surface, and smaller portions ammonium heteropoly acids are dispersed in carrier duct；On the other hand, long chain alkane
It is reacted under the conditions of high temperature, low hydrogen pressure, a large amount of carbon distributions can be generated on the carrier of catalyst, carrier can be weakened to a certain extent
Acidity, reduce support acidity position absorption ammonia quantity, so that heteropoly acid is mainly reacted with ammonium salt organic acid and generate heteropoly acid
It is evenly dispersed in carrier surface to facilitate ammonium heteropoly acids, and can remove above-mentioned carbon deposit through subsequent high-temperature roasting for ammonium salt, this
Sample effectively remains this Component Vectors acidic site.The catalyst that the method for the present invention obtains not only catalytic activity with higher,
And in the case where loading high-content, peracidity ammonium heteropoly acids, liquid hydrocarbon-selective with higher.
Specific embodiment
Below by embodiment, the present invention is described further, and reaction hydrocarbon raw material used in embodiment is to contain 525
The n-decane solution of μ g/g thiophene and 170 μ g/g pyridines.In the present invention, wt% is mass fraction.
Specific surface area, Kong Rong are measured using low temperature liquid nitrogen physisorphtion in the present invention, specifically use Merck & Co., Inc, the U.S.
The nitrogen absorption under low temperature instrument of ASAP2420 model measures；Detailed process: a small amount of sample is taken to be vacuum-treated 3 ~ 4h at 300 DEG C, most
Product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) afterwards and carries out nitrogen suction-desorption test.Wherein surface area is obtained according to BET equation
It arrives, pore-size distribution is obtained according to BJH model.SEM(scanning electron microscope) specifically using the JSM- of JEOL company, Japan production
The SEM(scanning electron microscope of 7500F type), it is equipped with EDAX-EDS, acceleration voltage: 20Kv, operating distance: 8mm, resolution ratio:
1nm。
Hydrogenation cracking activity indicates by the conversion ratio of n-decane, selectivity by " in product containing 5 carbon atoms and 5 with
The alkane molal quantity of upper carbon atom is divided by product total mole number " it indicates, it is denoted as C5 +Selectivity.This is because in general plus hydrogen
In process, it is desirable to which a pyrolysis product is more and second pyrolysis product is few, when being reaction hydrocarbon raw material with n-decane, in product
Alkane containing 5 carbon atoms and 5 or more carbon atom is all a pyrolysis product, so C5 +Selectivity characterizes one in product
The relative quantity of secondary pyrolysis product.
Embodiment 1
(1) preparation of Mo-Ni-P aqueous solution:
By 2.2 g phosphoric acid H3PO4(concentration 85wt%) is dissolved in 80mL water, and 8.1g molybdenum trioxide and 3.7g alkali formula is then added
Nickelous carbonate is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Ni-P aqueous solution after filtering.Wherein MoO3
Concentration be 0.08g/mL, the concentration of NiO is 0.02g/mL, and the concentration of P is 0.006 g/mL.
(2) preparation of catalyst:
By 100mL Mo-Ni-P aqueous solution, 10.4g phosphotungstic acid, 87.9g cetyl trimethylammonium bromide and 123.7g lemon
Lemon acid is made into mixed solution, and 182.4mL tetraethyl orthosilicate is added in mixed solution, stirs 2h, then stirs at 70 DEG C
It mixes at gel, by gel in aged at room temperature 12h, 8h is dried at 110 DEG C, then in 450 DEG C of roasting 3h, before catalyst is made
Body A, is then added in autoclave, and 450 DEG C are warming up under hydrogen atmosphere, handles 4h at 0.3MPa, is down to reaction temperature
500g n-decane solution is added in degree, and then adjusting Hydrogen Vapor Pressure to 0.5MPa, reacts 5 h at 400 DEG C, after reaction, will
Catalyst filtration comes out, and dries at room temperature to carrier surface without liquid phase, is then added to the aqueous solution containing 28.1g citric acid
In, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, at 60 DEG C after filtering
Lower drying；It is added in the aqueous solution containing 20.7g phosphotungstic acid, stirs at 70 DEG C and be evaporated to solution, obtained solid is existed
Then in 520 DEG C of roasting 3.0h catalyst is made, wherein MoO in 110 DEG C of dry 8.0h3Content is 8wt%, and NiO content is
2wt%, P content 0.6wt%, (NH4)0.2H2.8PW12O40Content is 30wt%.Catalyst property is listed in table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluation of catalyst:
After 0.5g catalyst to be packed into the isothermal section among reaction tube, it is passed through hydrogen, reaction system steps up pressure
The CS of % containing 2wt is passed through after inspection is air tight to 2.0 MPa2N-heptane solution, by reaction system be warming up to 320 DEG C vulcanization 3
H, after cut the n-decane liquid containing 525 μ g/g thiophene and 170 μ g/g pyridines, then reaction system is cooled to
300 DEG C, in 1500 h of hydrogen volume air speed-1Under, mass space velocity is 2.92 h-1, start to acquire sample, detection after reacting 1h
Catalyst hydrogenation cracking activity at reaction conditions and selectivity, the results are shown in Table 3.
Embodiment 2
(1) preparation of Mo-Ni-P aqueous solution:
By 3.0g phosphoric acid H3PO4(concentration 85wt%) is dissolved in 80mL water, and 10.1g molybdenum trioxide and 4.6g alkali formula is then added
Nickelous carbonate is warming up to 100 DEG C and is stirred at reflux 2.0h, and constant volume is 100mL to get Mo-Ni-P aqueous solution after filtering.Wherein MoO3
Concentration be 0.10 g/mL, the concentration of NiO is 0.025g/mL, and the concentration of P is 0.008 g/mL.
(2) preparation of catalyst:
By 100mL Mo-Ni-P aqueous solution, 18.1g phosphotungstic acid, 140.0g cetyl trimethylammonium bromide and 73.8g lemon
Lemon acid is made into mixed solution, and 174.9mL tetraethyl orthosilicate is added in mixed solution, stirs 2 h, then stirs at 70 DEG C
It mixes at gel, by gel in 12 h of aged at room temperature, catalysis is made then in 450 DEG C of 3 h of roasting in dry 8 h at 110 DEG C
Agent precursor A, is then added in autoclave, and 450 DEG C are warming up under hydrogen atmosphere, handles 4h at 0.3MPa, is down to anti-
Temperature is answered, 500g n-decane solution is added, Hydrogen Vapor Pressure is then adjusted to 0.5MPa, 5h is reacted at 400 DEG C, reaction terminates
Afterwards, catalyst filtration is come out, dries at room temperature to carrier surface without liquid phase, is then added to the water containing 40.6g citric acid
In solution, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, after filtering
It is dry at 60 DEG C；It is added in the aqueous solution containing 18.1g phosphotungstic acid, stirs at 70 DEG C and be evaporated to solution, consolidated what is obtained
In 110 DEG C of dry 8.0h, then in 500 DEG C of roasting 3.0h, catalyst is made, wherein MoO in body3Content is 10wt%, NiO content
For 2.5wt%, P content 0.8wt%, (NH4)0.5H2.5PW12O40Content is 35 wt%.Catalyst property is listed in table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluation of catalyst:
With embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table evaluating catalyst
3。
Embodiment 3
(1) preparation of Mo-Ni-P aqueous solution:
By 3.3 g phosphoric acid H3PO4(85 wt% of concentration) is dissolved in 80 mL water, and 12.1 g molybdenum trioxides and 5.6 are then added
G basic nickel carbonate is warming up to 100 DEG C and is stirred at reflux 2.0 h, and constant volume is 100 mL to get Mo-Ni-P aqueous solution after filtering.
Wherein MoO3Concentration be 0.12 g/mL, the concentration of NiO is 0.03 g/mL, and the concentration of P is 0.009 g/mL.
(2) preparation of catalyst:
By 100mL Mo-Ni-P aqueous solution, 27.6g phosphotungstic acid, 200.4g cetyl trimethylammonium bromide and 39.6g lemon
Lemon acid is made into mixed solution, and 156.1mL tetraethyl orthosilicate is added in mixed solution, stirs 2 h, then stirs at 70 DEG C
It mixes at gel, by gel in aged at room temperature 12h, catalyst is made then in 450 DEG C of 3 h of roasting in dry 8h at 110 DEG C
Precursor A, is then added in autoclave, and 450 DEG C are warming up under hydrogen atmosphere, handles 4h at 0.3MPa, is down to reaction
500g n-decane solution is added in temperature, and then adjusting Hydrogen Vapor Pressure to 0.5MPa, reacts 5h at 400 DEG C, after reaction,
Catalyst filtration is come out, dries at room temperature to carrier surface without liquid phase, is then added to the aqueous solution containing 48.1g citric acid
In, stirring to solution is evaporated at 70 DEG C；Obtained material, which is added in sal volatile, impregnates 10min, at 60 DEG C after filtering
Lower drying；It is added in the aqueous solution containing 13.8g phosphotungstic acid, stirs at 70 DEG C and be evaporated to solution, obtained solid is existed
Then in 470 DEG C of roasting 3.0h catalyst is made, wherein MoO in 110 DEG C of dry 8.0h3Content is 12wt%, and NiO content is
3.0wt%, P content 0.9wt%, (NH4)0.7H2.3PW12O40Content is 40wt%.Catalyst property is listed in table 1.
(3) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(4) evaluation of catalyst:
With embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table evaluating catalyst
3。
Embodiment 4
(1) preparation of catalyst:
In embodiment 3, cetyl trimethylammonium bromide is changed to 303.5g Cetyltrimethylammonium bromide,
Catalyst is made, wherein MoO in remaining same embodiment 33Content is 12wt%, and NiO content is 3.0wt%, P content 0.9wt%,
(NH4)0.7H2.3PW12O40Content is 40wt%.Catalyst property is listed in table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluation of catalyst:
With embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table evaluating catalyst
3。
Embodiment 5
(1) preparation of catalyst:
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 is made, wherein MoO3Content is 12wt%, and NiO content is 3.0wt%, P content 0.9wt%, (NH4)0.7H3.3SiW12O40Content is 40wt%.Catalyst property is listed in table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of silico-tungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluation of catalyst:
With embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table evaluating catalyst
3。
Embodiment 6
(1) preparation of catalyst:
In embodiment 3, n-decane solution being changed to hexadecane solution, catalyst is made with embodiment 3 in remaining,
Middle MoO3Content is 12wt%, and NiO content is 3.0wt%, P content 0.9wt%, (NH4)0.7H2.3PW12O40Content is 40wt%.It urges
Agent property is listed in table 1.
(2) catalyst characterization:
Elemental analysis is carried out to catalyst by SEM, the distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.
(3) evaluation of catalyst:
With embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table evaluating catalyst
3。
Comparative example 1
Compared with Example 3, without reduction treatment and long chain alkane processing step is added in catalyst precarsor A, will be catalyzed
Agent precursor A is added directly into the aqueous solution containing 48.1g citric acid, and stirring to solution is evaporated at 70 DEG C；Obtained material
It is added in sal volatile and impregnates 10min, it is dry at 60 DEG C after filtering；It is added to the aqueous solution containing 13.8g phosphotungstic acid
In, stirring to solution is evaporated at 70 DEG C, by obtained solid in 110 DEG C of dry 8.0h, then in 470 DEG C of roasting 3.0h, system
Catalyst is obtained, wherein MoO3Content is 12wt%, and NiO content is 3.0wt%, P content 0.9wt%, (NH4)0.7H2.3PW12O40Contain
Amount is 40wt%.Catalyst property is listed in table 1.The distribution situation of phosphotungstic acid ammonium salt on a catalyst is listed in table 2.Evaluating catalyst
With embodiment 1, catalyst hydrogenation cracking activity at reaction conditions and selectivity the results are shown in Table 3.
The property of 1 each catalyst of table
2 catalyst different location heteropoly acid ammonium salt content of table accounts for the percentage (wt%) of total content
The conversion ratio and selectivity of 3 each catalyst of table
Claims (21)
1. a kind of preparation method of hydrocracking catalyst, the hydrocracking catalyst includes acidic components, hydrogenation metal group
Divide and carrier, acidic components are ammonium heteropoly acids, hydrogenation metal component is Mo and Ni, and P is auxiliary agent, and carrier is silica；It is described
The preparation method of hydrocracking catalyst includes the following steps:
(1) it is prepared with molybdate compound, nickel compound containing, phosphorus-containing compound and water while nickeliferous, molybdenum, the cosolvency of phosphorus is water-soluble
Liquid；
(2) cosolvency aqueous solution, heteropoly acid and the template of nickeliferous, molybdenum, phosphorus that step (1) obtains are added to containing organic acid
In aqueous solution, mixed solution is obtained；
(3) silicon source is added in the solution that step (2) obtains and is uniformly mixed, then at 40~90 DEG C stirring at gel,
8.0~24.0h of aging at 30~50 DEG C；
(4) by step (3) resulting material in 90~120 DEG C of dry 3.0~12.0h, then 300~550 DEG C roast 2.0~
6.0h obtains catalyst precarsor A；
(5) the catalyst precarsor A that step (4) obtains is added in autoclave, it is restored in a hydrogen atmosphere
Processing；
(6) long chain alkane solution is driven into autoclave described in step (5), then adjust Hydrogen Vapor Pressure to normal pressure~
1MPa reacts 3.0~8.0h at 350~450 DEG C；
(7) the catalyst precarsor A after reaction in step (6) is filtered out, is dried at 30 DEG C~40 DEG C, until sample
Surface obtains catalyst precarsor B without liquid phase；
(8) the catalyst precarsor B that step (7) obtains is added in aqueous solutions of organic acids, is stirred at 40~90 DEG C to solution
It is evaporated, obtains catalyst precarsor C；
(9) the catalyst precarsor C that step (8) obtains is added in the alkaline solution containing ammonium, through filtering, is done at 40~90 DEG C
It is dry；Or the material that step (8) obtains is adsorbed into ammonia at 40~90 DEG C, obtain catalyst precarsor D；
(10) aqueous solution of heteropoly acid is added in the catalyst precarsor D that step (9) obtains, is stirred at 40~90 DEG C to molten
Liquid is evaporated；
(11) then the solid for obtaining step (10) roasts 2.0 at 300~550 DEG C at 90~120 DEG C of dry 3.0~12.0h
~6.0h is to get catalyst.
2. preparation method described in accordance with the claim 1, it is characterised in that: the ammonium heteropoly acids molecular formula is Hm(NH4)nYX12O40, 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.
3. preparation method described in accordance with the claim 1, it is characterised in that: molybdate compound described in step (1) is molybdenum oxide；
The nickel compound containing is basic nickel carbonate, and phosphorus-containing compound is phosphoric acid.
4. preparation method described in accordance with the claim 1, it is characterised in that: in step (1), nickeliferous, molybdenum, the cosolvency of phosphorus are water-soluble
Mo is in liquid with MoO3The concentration of meter is 0.03~0.2g/mL, and concentration of the Ni in terms of NiO is 0.005~0.08g/mL, the concentration of P
For 0.002~0.03g/mL.
5. preparation method described in accordance with the claim 1, it is characterised in that: template described in step (2) is dodecyl
Trimethylammonium bromide, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride,
One of Cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, hexamethylenetetramine are a variety of, the mould
Plate agent and step (3) silicon source are with SiO2The molar ratio of meter is 0.01~1.2.
6. preparation method described in accordance with the claim 1, it is characterised in that: heteropoly acid described in step (2) and step (10)
For one of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid or a variety of.
7. preparation method described in accordance with the claim 1, it is characterised in that: introduce heteropoly acid in step (2) and step (10)
Molar ratio is 3:1~1:3.
8. preparation method described in accordance with the claim 1, it is characterised in that: in step (2) organic acid be citric acid, tartaric acid,
One of malic acid is a variety of, and the organic acid and step (3) silicon source are with SiO2The molar ratio of meter is 0.1~1.2.
9. preparation method described in accordance with the claim 1, it is characterised in that: silicon source described in step (3) is ethyl orthosilicate
And/or silica solution.
10. preparation method described in accordance with the claim 1, it is characterised in that: reduction treatment process described in step (5) is such as
Under: catalyst precarsor is warming up to 300~600 DEG C under hydrogen atmosphere, 4.0~8.0h is handled at 0.1~0.5MPa.
11. preparation method according to claim 10, it is characterised in that: the hydrogen atmosphere is pure hydrogen or contains lazy
Property gas hydrogen, hydrogen volume concentration be 30%~100%.
12. preparation method described in accordance with the claim 1, it is characterised in that: long chain alkane described in step (6) be C10~
One of C16 long chain alkane is a variety of.
13. according to preparation method described in claim 1 or 12, it is characterised in that: long chain alkane described in step (6) is positive
One of decane, dodecane, hexadecane are a variety of.
14. preparation method described in accordance with the claim 1, it is characterised in that: the additional amount of long chain alkane described in step (6)
Mass ratio with catalyst precarsor A is 5:1~15:1.
15. preparation method described in accordance with the claim 1, it is characterised in that: organic acid described in step (8) is citric acid, wine
One of stone acid, malic acid are a variety of；SiO in the organic acid and catalyst precarsor B2Molar ratio be 0.05~
0.50。
16. preparation method described in accordance with the claim 1, it is characterised in that: in step (9), the solid that step (8) obtains is added
Enter and impregnated into the alkaline solution containing ammonia, dip time is 5~30min；The solid absorption ammonia that step (8) is obtained,
Adsorption time is 5~30 min.
17. preparation method described in accordance with the claim 1, it is characterised in that: the alkaline solution containing ammonium described in step (9) is
One of ammonium hydroxide, sal volatile, ammonium bicarbonate soln are a variety of.
18. preparation method described in accordance with the claim 1, it is characterised in that: ammonia described in step (9) using pure ammonia or
Person uses the mixed gas containing ammonia, and in mixed gas in addition to ammonia, other is one of inert gas, nitrogen or a variety of.
19. a kind of hydrocracking catalyst, it is characterised in that: the hydrocracking catalyst is using any in claim 1-18
The preparation of method described in claim.
20. hydrocracking catalyst according to claim 19, it is characterised in that: the hydrocracking catalyst includes acid
Property component, hydrogenation metal component and carrier, acidic components are ammonium heteropoly acids, hydrogenation metal component be Mo and Ni, P is auxiliary agent,
Carrier is silica；On the basis of the weight of catalyst, the content of acidic components is 30%~40%, MoO3Content is 5%~15%,
The content of NiO is 1%~5%, and P content is 0.5%~3%, and surplus is silica support；The property of the hydrocracking catalyst is such as
Under: specific surface area is 300~450 m20.40~0.55mL/g of/g, Kong Rongwei, average pore diameter are 4.5~6.3nm, heteropoly acid
Ammonium salt is distributed in 1.6wt%~4.7wt% of the catalyst center to the content in 1/4 radius for total content, is distributed in 1/4 half
Diameter is 4.7wt%~14.1wt% of total content to the content in 1/2 radius, is distributed in 1/2 radius to 3/4 radius
Content be total content 7.8wt%~23.4wt%, the content being distributed within the scope of 3/4 radius to catalyst external surface is always contains
57.8wt%~85.9wt% of amount.
21. hydrocracking catalyst according to claim 20, it is characterised in that: the ammonium heteropoly acids molecular formula is Hm
(NH4)nYX12O40, 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；Work as Y
When representing P, m+n=3, n value is 0.1~1.0.
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| CN109926073B (en) * | 2017-12-15 | 2021-10-08 | 中国石油化工股份有限公司 | High-selectivity hydrocracking catalyst and preparation method thereof |
| CN109926093B (en) * | 2017-12-15 | 2021-10-08 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN109926094B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN115414952B (en) * | 2022-08-22 | 2023-09-12 | 中国五环工程有限公司 | Multicomponent hydrogenation catalyst for synthesizing methyl glycolate and preparation method thereof |
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