CN106944079B - A kind of preparation method of iso-butane preparing isobutene catalyst - Google Patents
A kind of preparation method of iso-butane preparing isobutene catalyst Download PDFInfo
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- CN106944079B CN106944079B CN201610003109.XA CN201610003109A CN106944079B CN 106944079 B CN106944079 B CN 106944079B CN 201610003109 A CN201610003109 A CN 201610003109A CN 106944079 B CN106944079 B CN 106944079B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 186
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 86
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000001282 iso-butane Substances 0.000 title claims abstract description 35
- 235000013847 iso-butane Nutrition 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 48
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 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
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 229910052720 vanadium Inorganic materials 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- 239000000806 elastomer Substances 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229920003169 water-soluble polymer Polymers 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 9
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 229910015234 MoCo Inorganic materials 0.000 description 8
- 229920000609 methyl cellulose Polymers 0.000 description 8
- 239000001923 methylcellulose Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 229910019923 CrOx Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JEAKTLDJVSMBKC-UHFFFAOYSA-N 2-methylpropane;2-methylprop-1-ene Chemical compound CC(C)C.CC(C)=C JEAKTLDJVSMBKC-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910005809 NiMoO4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910017850 Sb—Ni Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- LBPYPRXFFYUUSI-UHFFFAOYSA-N furan-2-carbaldehyde;hydrate Chemical compound O.O=CC1=CC=CO1 LBPYPRXFFYUUSI-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010792 warming Methods 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
- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium 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
- B01J23/8885—Tungsten containing also 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/888—Tungsten
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of iso-butane preparing isobutene catalyst, the catalyst includes the first active component, the second active component, auxiliary agent and carrier；The preparation method of the catalyst includes the following steps: to prepare catalyst precarsor A first, then reduction treatment is carried out to catalyst precarsor A, solution B is uniformly mixed with furfural aqueous solution and is added in autoclave together with catalyst precarsor A, it is reacted after solution C is added, filtering obtained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.The catalyst reaction activity of this method preparation is high, not only reduces metal consumption, but also improve the selectivity of isobutene.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst of preparing isobutene, more particularly, to a kind of iso-butane preparing isobutene
Loaded catalyst preparation method.
Background technique
With the development of petrochemical technology, isobutene has become in alkene the most important basis in addition to ethylene, propylene
Industrial chemicals.Using isobutene as the development of the downstream product of resource, increase China to the demand of isobutene rapidly.
Iso-butane is mainly derived from petroleum catalytic cracking production process, the demand day with refinery to maximization of economic benefit
It is becoming tight urgent, iso-butane produces isobutene project and causes to pay attention to extensively.Currently, industrially mainly being produced using catalytic dehydrogenation of isobutane
Isobutene.The method of preparing isobutene through dehydrogenation of iso-butane, exists the problems such as being easy carbon distribution due to reaction temperature height and catalyst surface
Not the problems such as target product selectivity is not high and catalyst easy in inactivation.The method of producing isobutene from oxidative dehydrogenation of isobutane, although also
In conceptual phase, but the advantages of this method is: oxidative dehydrogenation is not limited by thermodynamical equilibrium, and there is no catalyst
Carbon distribution problem, and the reaction is exothermic reaction, can be carried out at a lower temperature, it is energy saving.
Currently, for isobutene for oxo-dehydrogenation reaction catalyst mainly include catalytic component based on vanadium, catalyst with base of molybdenum and its
Its type catalyst.Wherein, catalytic component based on vanadium catalytic activity usually with higher.Using vanadium as the 10%V-UVM-7 of active component
Catalyst, iso-butane conversion ratio at 490 DEG C are 12%, and selective isobutene is 41%(Catal. Today, 2006:, 117:
180).V-Sb-Ni/Al2O3Iso-butane conversion ratio of the catalyst at 550 DEG C is 46%, selective isobutene 66%(Appl.
Catal. A, 2003,250:143).Composite oxides Mg containing vanadium1.8V2Co0.2OxAlso there is preferable catalytic performance, 450
DEG C when iso-butane conversion ratio be 8.4%, the selectivity of isobutene is 86%(J. Jpn. Petrol. Inst., 2003,46:
87).The catalyst with base of molybdenum of dehydrogenation of isobutane reaction is mainly NiMoO4Catalyst, iso-butane of this catalyst at 500 DEG C
Conversion ratio is 8%, selective isobutene be 40%(Appl. Catal. A, 1998,166:L259).NiMoO is modified with K, Ca, P4
The selectivity for generating isobutene, such as K-NiMoO can be improved in catalyst4Iso-butane conversion ratio of the catalyst at 480 DEG C is 8%,
Selective isobutene is about 70%(Appl. Catal. A, and 1998,169:L3).In addition, related isobutene for oxo-dehydrogenation catalytic body
System further relates to Cr-Ce-O, heteropolyacid salt and RE phosphate etc..
CN101618319A discloses a kind of CrOx/ mesoporous CaO catalyst of efficient producing isobutene from oxidative dehydrogenation of isobutane,
When reaction temperature is 500 DEG C, selective isobutene is 81% on 10%CrOx/ mesoporous CaO catalyst, and iso-butane conversion ratio is
10%.CN101439292A discloses a kind of solid catalyst of producing isobutene from oxidative dehydrogenation of isobutane, and the major ingredient of the catalyst is
Phosphato-molybdic heteropolyacid alkali metal (alkaline-earth metal) salt-nickel oxide composite material, additive be silica, titanium oxide, vanadic anhydride,
One of copper oxide, cobaltosic oxide, cerium oxide, tellurium oxide etc., at reaction temperature be 300~600 DEG C, iso-butane turns
Rate is 7%~31%, and isobutene yield is up to 6%~18%.
However, the target product and iso-butane of isobutene for oxo-dehydrogenation reaction are easy to happen under oxygen existence condition
Deep oxidation leads to problems such as the waste of raw material and target product selectivity lower.Producing isobutene from oxidative dehydrogenation of isobutane reaction
Or fast reaction (this fast reaction be typically at carry out under conditions of mass transport limitation), reactant is urged in arrival
Reaction is completed while agent outer surface, thus the inner surface of catalyst contributes less goal response, this is resulted in
Lower metal utilization in carrier duct increases catalyst cost, while can also accelerate the deep oxidation of product.Therefore,
The catalyst for researching and developing a kind of high conversion and highly selective producing isobutene from oxidative dehydrogenation of isobutane is of great significance.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of preparations of iso-butane preparing isobutene catalyst
Method.Mo and alumina support in useless hydrotreating catalyst is not only utilized in this method, but also takes full advantage of useless plus hydrogen
The Ni and V deposited on processing catalyst, solves the pollution problem of dead catalyst, and economize on resources, improve benefit, in technology
It is upper to be easy to implement, resulting producing isobutene from oxidative dehydrogenation of isobutane catalyst have low in cost, metal component utilization rate height with
And the feature that selectivity is good.
The present invention provides a kind of preparation method of iso-butane preparing isobutene catalyst, the catalyst includes the first activity
Component, the second active component, auxiliary agent and carrier；First active component be Ni, the second active component be V, auxiliary agent W, Mg,
One or more of Ca, K, Cr, Ce or La, preferably W, carrier are aluminium oxide；Catalysis is accounted for each element quality in catalyst
On the basis of the percentage of agent quality, the content of the first active component Ni is 1wt%~5wt%, and the content of the second active component V is
The content of 5wt%~10wt%, auxiliary agent are 1wt%~6wt%, and surplus is carrier；The preparation method of the catalyst includes following step
It is rapid:
(1) waste residue oil hydrogenation catalysts are subjected to the oil and carbon deposit that pretreatment removes surface；
(2) pretreated waste residue oil hydrogenation catalysts are ground；
(3) it is molten that aluminum hydroxide solid elastomer, binder, the first active component presoma and acid is added in the powder in step (2)
Liquid, then kneading, molding；
(4) by sample obtained in step (3) in 80 ~ 120 DEG C of dry 3 ~ 12h, then in 300 ~ 600 DEG C of 2 ~ 6h of roasting,
Obtain catalyst precarsor A；
(5) reduction treatment is carried out to the catalyst precarsor A that step (4) obtains using reducing atmosphere；
(6) auxiliary agent presoma is soluble in water, obtain solution B, and be uniformly mixed with furfural aqueous solution, then with step
(5) the catalyst precarsor A obtained is added in autoclave together；
(7) water soluble polymer, the second active component presoma is soluble in water, obtain solution C；By solution C
Be added in autoclave described in step (6), replaced 2~5 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 2~
4MPa reacts 1~3h at 100~200 DEG C；
(8) solidliquid mixture obtained to step (7) is down to 20 ~ 30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added, puts
1~2h is set, is then filtered, obtained solid sample after drying, calcination process, obtains catalyst again.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, the waste residue oil hydrogenation catalysts are with aluminium oxide
For carrier, active metal component contains Mo and Co, is that former reaction has been not achieved to require, or without complete due to gradation
The residual oil hydrocatalyst used in the fixed bed or ebullated bed of inactivation；The dead catalyst due to be in hydrogenation process it is used
Hydrotreating catalyst generally have part metals Ni and V deposition so in hydrogenation process；The pretreatment can
To use solvent extraction process, then through dry and roasting.The extraction solvent generally used is one of petroleum ether, toluene or two
Kind.Dry and roasting condition is as follows: dry 5 ~ 12h at 80 ~ 120 DEG C roasts 2 ~ 6h at 400 ~ 700 DEG C.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, waste residue oil hydrogenation catalysts described in step (2)
It grinds to more than 120 mesh, more than preferably 200 mesh.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, oxygen in aluminum hydroxide solid elastomer described in step (3)
The mass fraction for changing aluminium is 60% ~ 80%, and the additional amount of the aluminum hydroxide solid elastomer is according to dead catalyst and final catalyst
It is required that being added；The first active component presoma is soluble metal nickel salt solution, is specifically as follows nickel nitrate solution or second
The additional amount of sour nickel solution, nickel is added according to the requirement of dead catalyst and final catalyst, the soluble metal nickel salt of addition
Water in solution is the 75wt% ~ 85wt% of the sum of dead catalyst weight and aluminum hydroxide solid elastomer weight；The acid solution be hydrochloric acid,
The one or more of sulfuric acid, nitric acid, citric acid, acetic acid, phosphoric acid, boric acid, preferably acetic acid or nitric acid；The concentration of the acid solution
Generally 0.2 ~ 5.0mol/L, the quality that acid solution is added is 3wt% ~ 20wt% of dead catalyst weight；The binder is normal
Binder, such as high molecular polymer are advised, content is 2wt% ~ 12wt% of waste residue oil hydrogenation catalysts weight.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, Mo in catalyst precarsor A described in step (4)
Content be 1wt% ~ 3wt%, the content of V is 0.1wt% ~ 1wt%, and the content of Ni is 1wt% ~ 5wt%.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, reducing atmosphere described in step (5) is hydrogen
Or the mixed gas of hydrogen and nitrogen, the volumn concentration of hydrogen is 10%~95% in the mixed gas.It is specific to go back
Former treatment process is as follows: catalyst precarsor being warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen and nitrogen
The mixed gas of gas, in 0.1~0.5MPa(absolute pressure) processing 4~8h after, be down to room temperature in a nitrogen atmosphere.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, auxiliary agent presoma described in step (6) is tungsten
One of sour ammonium, magnesium nitrate, calcium nitrate, potassium nitrate, chromic nitrate, cerous nitrate, lanthanum nitrate are a variety of, preferably ammonium tungstate；Institute
It states in solution B, based on the element, the mass fraction in solution B is 1%~6% to auxiliary agent；The quality of furfural in the furfural aqueous solution
Score is 30%~50%；Furfural aqueous solution described in step (6) and the mass ratio of solution B are 3 ~ 5, the solution B and furfural water
The mass ratio for the reduction rear catalyst precursor A that the gross mass of solution and step (5) obtain is 3~6.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, the polymerization of water soluble polymer described in step (7)
Object is one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA)；Described second is living
Property component presoma be ammonium metavanadate and/or vanadic sulfate, preferably ammonium metavanadate；In the solution C, before the second active component
Driving contained vanadium in body, the mass fraction in solution C is 0.1%~2% based on the element, and water soluble polymer is in solution C
Mass fraction be 3~6 times of V element mass fraction.
In the preparation method of iso-butane preparing isobutene catalyst of the present invention, addition dehydrated alcohol or lemon described in step (8)
The quality of lemon acid and the mass ratio of water soluble polymer are 2 ~ 4；The mass fraction of the aqueous citric acid solution be 10%~
20%；The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h；It is described
Maturing temperature is 500~900 DEG C, and preferably 600~800 DEG C, calcining time is 2~12h, preferably 4~8h.
The catalyst of the method for the present invention preparation is reacted applied to producing isobutene from oxidative dehydrogenation of isobutane, preferable process conditions
Are as follows: the composition i-C of unstripped gas4H10/O2Molar ratio is 0.5~1, can contain Ar, N in unstripped gas2Or the dilution property gas such as He,
3000~9000mLg of unstripped gas air speedcat -1·h-1, reaction pressure is normal pressure, and reaction temperature is 500~700 DEG C.
Compared with prior art, a kind of available active metal outer layer distribution of the preparation method being related to through the invention
Catalyst for producing isobutene from oxidative dehydrogenation of isobutane.In the present invention, chaff is carried out using waste residue oil hydrogenating treatment catalyst
Aldehyde water phase hydrogenation reaction.Active metal predecessor and water soluble polymer is added simultaneously in the system of furfural hydrogenation,
On the one hand hinder active metal to the diffusion inside catalyst granules using furfural hydrogenation product；On the other hand, active gold is utilized
Belong to the coordination between predecessor and water soluble polymer, active metallic ion is in catalyst granules in reduction solution
Inside and outside concentration difference slows down active metal to the diffusion velocity inside catalyst granules.The catalyst reaction of this method preparation is living
Property it is high, not only reduced metal consumption, but also improve the selectivity of isobutene.Catalyst precarsor processing simultaneously and catalyst preparation one
Step is completed, and preparation process is simple, is conducive to industrial amplification.
Specific embodiment
Technology contents and effect of the invention are further illustrated below with reference to embodiment, but are not so limited the present invention.
Evaluation condition: isobutene for oxo-dehydrogenation reaction carries out on atmospheric fixed bed micro-reaction equipment, catalyst loading
0.2g, 650 DEG C of reaction temperature, reaction gas forms i-C4H10/O2/N2=1/1/4(molar ratio), flow velocity: 20mL/min, air speed
6000mL·gcat -1·h-1, product is after condensation water removal with gas chromatograph on-line analysis.Reaction starts sampling point after 1 hour
Analysis, evaluation results are shown in Table 1.
The metal element content in catalyst is determined using XRF analysis technology.Using scanning electron microscope analysis institute of the present invention
The distribution situation of active component on a catalyst in the catalyst of preparation.Catalyst activity obtained by the embodiment of the present invention and comparative example
The scanning electron microscope analysis of component vanadium the results are shown in Table 2.
Embodiment 1
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 740g is added and methylcellulose 7g, addition contain
The aqueous solution 700mL of 85.72g Nickelous nitrate hexahydrate adds 1.0mol/L nitric acid solution 10mL, after mixing in banded extruder
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made, wherein Mo is accounted for urge based on the element in upper extruded moulding
Agent precursor A weight 2wt%, Ni account for catalyst precarsor A weight 3wt% based on the element；By 20g catalyst precarsor A in hydrogen
Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), reduction
Time 4h；0.69g ammonium tungstate is dissolved in 15mL deionized water, solution B is obtained, and is 40% with the mass fraction of its 4 times of quality
Furfural aqueous solution be uniformly mixed, be then added in autoclave together with the catalyst precarsor A after reduction activation；By 9g
Polyethylene glycol, 4.41g ammonium metavanadate are dissolved in 200mL deionized water, obtain solution C；Solution C is also added to autoclave
In, it is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To in above-mentioned autoclave
Solidliquid mixture after reaction is down to 25 DEG C, and 27g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample is put into
6h is dried in baking oven at 110 DEG C, roasts 6h at 700 DEG C, obtaining quality based on the element and accounting for catalyst percentage composition is 2.5%
The catalyst of Ni, 6.7%V, 1.4%W, are denoted as C-1.
Embodiment 2
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 1666g is added and methylcellulose 10g, addition contain
There is the aqueous solution 1500mL of 54.01g Nickelous nitrate hexahydrate, add 1.0mol/L nitric acid solution 20mL, is squeezing after mixing
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made in extruded moulding on machine, and wherein Mo is based on the element
It accounts for catalyst precarsor A weight 1wt%, Ni and accounts for catalyst precarsor A weight 1wt% based on the element；By 20g catalyst precarsor A hydrogeneous
Activated in the mixed atmosphere of gas, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure),
Recovery time 4h；0.34g ammonium tungstate is dissolved in 15mL deionized water, solution B, and the mass fraction with its 4 times of quality are obtained
It is uniformly mixed for 40% furfural aqueous solution, is then added to autoclave together with the catalyst precarsor A after reduction activation
In；6g polyethylene glycol, 2.8g ammonium metavanadate are dissolved in 200mL deionized water, solution C is obtained；Solution C is also added to high pressure
It in reaction kettle, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To above-mentioned height
Solidliquid mixture after reacting in pressure kettle is down to 25 DEG C, and 18g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample
Product are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for catalyst percentage composition
For 0.7%Ni, the catalyst of 3.9%V, 0.6%W are denoted as C-2.
Embodiment 3
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 431g is added and methylcellulose 5g, addition contain
The aqueous solution 400mL of 96.3g Nickelous nitrate hexahydrate adds 1.0mol/L nitric acid solution 10mL, after mixing in banded extruder
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made, wherein Mo is accounted for urge based on the element in upper extruded moulding
Agent precursor A weight 3wt%, Ni account for catalyst precarsor A weight 5wt% based on the element；By 20g catalyst precarsor A in hydrogen
Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), reduction
Time 4h；1.03g ammonium tungstate is dissolved in 15mL deionized water, solution B is obtained, and is 40% with the mass fraction of its 4 times of quality
Furfural aqueous solution be uniformly mixed, be then added in autoclave together with the catalyst precarsor A after reduction activation；It will
11g polyethylene glycol, 5.47g ammonium metavanadate are dissolved in 200mL deionized water, obtain solution C；It is anti-that solution C is also added to high pressure
It answers in kettle, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To above-mentioned high pressure
Solidliquid mixture after reacting in kettle is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample
It is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, quality based on the element is obtained and accounts for catalyst percentage composition and be
The catalyst of 4.3%Ni, 8.8%V, 1.5%W, are denoted as C-3.
Embodiment 4
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 740g is added and methylcellulose 10g, addition contain
The aqueous solution 700mL of 85.72g Nickelous nitrate hexahydrate adds 1.0mol/L nitric acid solution 10mL, after mixing in banded extruder
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made, wherein Mo is accounted for urge based on the element in upper extruded moulding
Agent precursor A weight 2wt%, Ni account for catalyst precarsor A weight 3wt% based on the element；By 20g catalyst precarsor A in hydrogen
Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), reduction
Time 4h；5.34g magnesium nitrate is dissolved in 15mL deionized water, solution B is obtained, and is 30% with the mass fraction of its 3 times of quality
Furfural aqueous solution be uniformly mixed, be then added in autoclave together with the catalyst precarsor A after reduction activation；By 9g
Polyethylene glycol, 4.45g ammonium metavanadate are dissolved in 200mL deionized water, obtain solution C；Solution C is also added to autoclave
In, it is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To in above-mentioned autoclave
Solidliquid mixture after reaction is down to 25 DEG C, and 27g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample is put into
6h is dried in baking oven at 110 DEG C, roasts 6h at 700 DEG C, obtaining quality based on the element and accounting for catalyst percentage composition is 2.3%
The catalyst of Ni, 6.3%V, 1.5%Mg, are denoted as C-4.
Embodiment 5
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 740g is added and methylcellulose 5g, addition contain
The aqueous solution 700mL of 85.72g Nickelous nitrate hexahydrate adds 1.0mol/L nitric acid solution 8mL, after mixing in banded extruder
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made, wherein Mo is accounted for urge based on the element in upper extruded moulding
Agent precursor A weight 2wt%, Ni account for catalyst precarsor A weight 3wt% based on the element；By 20g catalyst precarsor A in hydrogen
Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), reduction
Time 4h；1.29g potassium nitrate is dissolved in 15mL deionized water, solution B is obtained, and is 50% with the mass fraction of its 5 times of quality
Furfural aqueous solution be uniformly mixed, be then added in autoclave together with the catalyst precarsor A after reduction activation；By 9g
Polyethylene glycol, 4.45g ammonium metavanadate are dissolved in 200mL deionized water, obtain solution C；Solution C is also added to autoclave
In, it is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To in above-mentioned autoclave
Solidliquid mixture after reaction is down to 25 DEG C, and 27g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample is put into
6h is dried in baking oven at 110 DEG C, roasts 6h at 700 DEG C, obtaining quality based on the element and accounting for catalyst percentage composition is 2.6%
The catalyst of Ni, 6.2%V, 1.5%K, are denoted as C-5.
Embodiment 6
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 740g is added and methylcellulose 7g, addition contain
The aqueous solution 700mL of 85.72g Nickelous nitrate hexahydrate adds 1.0mol/L nitric acid solution 10mL, after mixing in banded extruder
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made, wherein Mo is accounted for urge based on the element in upper extruded moulding
Agent precursor A weight 2wt%, Ni account for catalyst precarsor A weight 3wt% based on the element；By 20g catalyst precarsor A in hydrogen
Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), reduction
Time 4h；3.85g cadmium nitrate is dissolved in 15mL deionized water, solution B is obtained, and is 40% with the mass fraction of its 4 times of quality
Furfural aqueous solution be uniformly mixed, be then added in autoclave together with the catalyst precarsor A after reduction activation；By 9g
Polyvinyl alcohol, 4.45g ammonium metavanadate are dissolved in 200mL deionized water, obtain solution C；Solution C is also added to autoclave
In, it is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To in above-mentioned autoclave
Solidliquid mixture after reaction is down to 25 DEG C, and 27g dehydrated alcohol is added, and places 1.5h, then filters, obtained solid sample is put into
6h is dried in baking oven at 110 DEG C, roasts 6h at 700 DEG C, obtaining quality based on the element and accounting for catalyst percentage composition is 2.2%
The catalyst of Ni, 6.1%V, 1.5%Cr, are denoted as C-6.
Embodiment 7
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 740g is added and methylcellulose 7g, addition contain
The aqueous solution 700mL of 85.72g Nickelous nitrate hexahydrate adds 1.0mol/L nitric acid solution 10mL, after mixing in banded extruder
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made, wherein Mo is accounted for urge based on the element in upper extruded moulding
Agent precursor A weight 2wt%, Ni account for catalyst precarsor A weight 3wt% based on the element；By 20g catalyst precarsor A in hydrogen
Activated in mixed atmosphere, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa(absolute pressure), reduction
Time 4h；1.56g lanthanum nitrate is dissolved in 15mL deionized water, solution B is obtained, and is 40% with the mass fraction of its 4 times of quality
Furfural aqueous solution be uniformly mixed, be then added in autoclave together with the catalyst precarsor A after reduction activation；By 9g
Polyvinylpyrrolidone (k30), 4.45g ammonium metavanadate are dissolved in 200mL deionized water, obtain solution C；Solution C is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the aqueous citric acid solution that 180g mass fraction is 15% is added, puts
Set 1.5h, then filter, obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtain with
It is 2.6%Ni that element meter quality, which accounts for catalyst percentage composition, and the catalyst of 6.9%V, 1.6%La are denoted as C-7.
Comparative example
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is removed by extracting
Oil on catalyst surface, in 110 DEG C of dry 8h, gained catalyst is in 450 DEG C of roasting 4h, and dead catalyst (contains after being handled
Mo:12.8wt%, Co:2.3 wt%, V:2.5wt%, Ni:1.9 wt%, Al2O3: 71.2 wt%), catalyst is ground to 200 mesh
(referring to through 200 meshes) weighs powder weight 100g, and aluminum hydroxide solid elastomer 740g is added and methylcellulose 7g, addition contain
The aqueous solution 700mL of 85.72g Nickelous nitrate hexahydrate adds 1.0mol/L nitric acid solution 10mL, after mixing in banded extruder
In 110 DEG C of dry 8h, then in 400 DEG C of roasting 3h, catalyst precarsor A is made, wherein Mo is accounted for urge based on the element in upper extruded moulding
Agent precursor A weight 2wt%, Ni account for catalyst precarsor A weight 3wt% based on the element；By 20g catalyst precarsor A be added to containing
0.69g ammonium tungstate, 4.45g ammonium metavanadate aqueous solution in, be evaporated in 80 DEG C of stirrings to solution, be put into baking oven at 110 DEG C
6h is dried, roasts 6h at 700 DEG C, obtaining quality based on the element and accounting for catalyst percentage composition is 2.5% Ni, 7.3%V, 1.7%W
Catalyst, be denoted as D-1.
The reactivity worth of 1 catalyst of table
2 catalyst activity component V content of table is distributed (wt%)
Claims (32)
1. a kind of preparation method of iso-butane preparing isobutene catalyst, the catalyst includes the first active component, the second activity
Component, auxiliary agent and carrier；First active component be Ni, the second active component be V, auxiliary agent W, Mg, Ca, K, Cr, Ce or
One or more of La, carrier are aluminium oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst,
The content of first active component Ni is 1wt%~5wt%, and the content of the second active component V is 5wt%~10wt%, the content of auxiliary agent
For 1wt%~6wt%, surplus is carrier；The preparation method of the catalyst includes the following steps:
(1) waste residue oil hydrogenation catalysts are subjected to the oil and carbon deposit that pretreatment removes surface；
(2) the pretreated waste residue oil hydrogenation catalysts of step (1) are ground；
(3) aluminum hydroxide solid elastomer, binder, the first active component presoma and acid solution is added in the powder in step (2), so
Kneading, molding afterwards；
(4) it by sample obtained in step (3) in 80 ~ 120 DEG C of dry 3 ~ 12h, then in 300 ~ 600 DEG C of 2 ~ 6h of roasting, obtains
Catalyst precarsor A；
(5) reduction treatment is carried out to the catalyst precarsor A that step (4) obtains using reducing atmosphere；
(6) auxiliary agent presoma is soluble in water, solution B is obtained, and be uniformly mixed with furfural aqueous solution, is then obtained with step (5)
To catalyst precarsor A be added in autoclave together；
(7) water soluble polymer, the second active component presoma is soluble in water, obtain solution C；Solution C is added
It into autoclave described in step (6), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C, the water soluble polymer is polyethylene glycol (PEG), polyvinylpyrrolidone
(PVP), one or more of polyvinyl alcohol (PVA)；
(8) solidliquid mixture obtained to step (7) is down to 20 ~ 30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added, and places 1
~2h, is then filtered, and obtained solid sample after drying, calcination process, obtains catalyst again.
2. according to the method for claim 1, it is characterised in that: the auxiliary agent is W.
3. according to the method for claim 1, it is characterised in that: waste residue oil hydrogenation catalysts as described in step (1) are with oxygen
Change aluminium is carrier, and active metal component contains Mo and Co.
4. according to the method for claim 1, it is characterised in that: pretreatment described in step (1) uses solvent extraction process, so
Dry afterwards and roasting, the extraction solvent used is one or both of petroleum ether, toluene.
5. according to the method for claim 4, it is characterised in that: the drying and roasting condition are as follows: at 80 ~ 120 DEG C
Dry 5 ~ 12h, roasts 2 ~ 6h at 400 ~ 700 DEG C.
6. according to the method for claim 1, it is characterised in that: waste residue oil hydrogenation catalysts grounds travel described in step (2)
It is broken to 120 mesh or more.
7. according to method described in claim 1 or 6, it is characterised in that: the grinding of waste residue oil hydrogenation catalysts described in step (2)
It is crushed to 200 mesh or more.
8. according to the method for claim 1, it is characterised in that: aluminium oxide in aluminum hydroxide solid elastomer described in step (3)
Mass fraction is 60% ~ 80%.
9. according to the method for claim 1, it is characterised in that: the first active component presoma described in step (3) is can
Solube metallic nickel salt solution.
10. according to the method for claim 1, it is characterised in that: the first active component presoma described in step (3) is nitre
Sour nickel solution or Ni-acetate solution.
11. according to the method for claim 9, it is characterised in that: the water in the soluble metal nickel salt solution is useless urge
75wt% ~ 85wt% of the sum of agent weight and aluminum hydroxide solid elastomer weight.
12. according to the method for claim 1, it is characterised in that: acid solution described in step (3) is hydrochloric acid, sulfuric acid, nitre
The one or more of acid, citric acid, acetic acid, phosphoric acid, boric acid.
13. according to method described in claim 1 or 12, it is characterised in that: acid solution described in step (3) is acetic acid or nitre
Acid.
14. according to the method for claim 1, it is characterised in that: the concentration of acid solution described in step (3) be 0.2 ~
5.0mol/L。
15. according to the method for claim 1, it is characterised in that: the binder content is waste residue oil hydrogenation catalysts weight
2wt% ~ 12wt% of amount.
16. according to the method for claim 1, it is characterised in that: Mo's contains in catalyst precarsor A described in step (4)
Amount is 1wt% ~ 3wt%, and the content of V is 0.1wt% ~ 1wt%, and the content of Ni is 1wt% ~ 5wt%.
17. according to the method for claim 1, it is characterised in that: reducing atmosphere described in step (5) is hydrogen or hydrogen
The mixed gas of gas and nitrogen, the volumn concentration of hydrogen is 10%~95% in the mixed gas.
18. according to the method for claim 1, it is characterised in that: auxiliary agent presoma described in step (6) be ammonium tungstate,
One of magnesium nitrate, calcium nitrate, potassium nitrate, chromic nitrate, cerous nitrate, lanthanum nitrate are a variety of.
19. according to method described in claim 1 or 18, it is characterised in that: auxiliary agent presoma described in step (6) is wolframic acid
Ammonium.
20. according to the method for claim 1, it is characterised in that: in solution B described in step (6), auxiliary agent based on the element,
Mass fraction in solution B is 1%~6%.
21. according to the method for claim 1, it is characterised in that: the quality of furfural in furfural aqueous solution described in step (6)
Score is 30%~50%.
22. according to the method for claim 1, it is characterised in that: the matter of furfural aqueous solution and solution B described in step (6)
Amount is than being 3 ~ 5.
23. according to the method for claim 1, it is characterised in that: solution B described in step (6) and furfural aqueous solution it is total
The mass ratio for the reduction rear catalyst precursor A that quality and step (5) obtain is 3~6.
24. according to the method for claim 1, it is characterised in that: the second active component presoma is inclined described in step (7)
Ammonium vanadate and/or vanadic sulfate.
25. according to method described in claims 1 or 24, it is characterised in that: the second active component presoma described in step (7)
For ammonium metavanadate.
26. according to the method for claim 1, it is characterised in that: in solution C described in step (7), before the second active component
Driving contained vanadium in body, the mass fraction in solution C is 0.1%~2% based on the element, and water soluble polymer is in solution C
Mass fraction be 3~6 times of V element mass fraction.
27. according to the method for claim 1, it is characterised in that: addition dehydrated alcohol or citric acid described in step (8)
The mass ratio of quality and water soluble polymer is 2 ~ 4.
28. according to the method for claim 1, it is characterised in that: the mass fraction of aqueous citric acid solution described in step (8)
It is 10%~20%.
29. according to the method for claim 1, it is characterised in that: drying temperature described in step (8) is 70~150 DEG C, is done
The dry time is 2~12h.
30. according to method described in claims 1 or 29, it is characterised in that: drying temperature described in step (8) is 80~120
DEG C, drying time is 4~8h.
31. according to the method for claim 1, it is characterised in that: maturing temperature described in step (8) is 500~900 DEG C,
Calcining time is 2~12h.
32. according to method described in claim 1 or 31, it is characterised in that: maturing temperature described in step (8) is 600~800
DEG C, calcining time is 4~8h.
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