CN105363461B - 一种水热合成油品加氢催化剂的方法 - Google Patents
一种水热合成油品加氢催化剂的方法 Download PDFInfo
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- CN105363461B CN105363461B CN201510657609.0A CN201510657609A CN105363461B CN 105363461 B CN105363461 B CN 105363461B CN 201510657609 A CN201510657609 A CN 201510657609A CN 105363461 B CN105363461 B CN 105363461B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000010953 base metal Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000001433 sodium tartrate Substances 0.000 claims description 5
- 235000011004 sodium tartrates Nutrition 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- -1 neopelex Chemical compound 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 4
- 229960002167 sodium tartrate Drugs 0.000 claims description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 2
- 229940082004 sodium laurate Drugs 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007493 shaping process Methods 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 235000015165 citric acid Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 238000002242 deionisation method Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- HELHAJAZNSDZJO-UHFFFAOYSA-L sodium tartrate Chemical class [Na+].[Na+].[O-]C(=O)C(O)C(O)C([O-])=O HELHAJAZNSDZJO-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/883—Molybdenum and nickel
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
本发明公开了一种水热合成油品加氢催化剂的方法，其步骤包括：配制含有至少一种Ⅷ族非贵金属盐和至少一种ⅥB族金属盐的酸性溶液，与含有尿素、表面活性剂的活性氧化铝的浆料共同加入高压反应釜进行水热反应，随后经洗涤、干燥、成型、焙烧制得高活性的加氢催化剂。采用该方法制备的加氢催化剂具有大的比表面积、孔容和孔径，具有高的加氢活性，特别适用于具有芳烃含量高、氮含量高、硫含量高、分子大等特点的烃类的加氢精制过程，本方法操作简单，反应条件易控，适合工业放大生产。
Description
技术领域
本发明属于加氢催化剂制备技术领域，涉及一种水热法合成高活性加氢催化剂的制备方法。
背景技术
为保护环境和人体健康，世界各国均在不断提高油品质量标准，同时原油日益劣质化与重质化，为了充分利用有限资源，炼油工业需要更有效的处理技术，其中加氢工艺成为改善油品质量最有效的手段之一，同时对使用的加氢催化剂提出了更高的要求。一方面，加氢催化剂的活性组分要有高的活性保证能够深度脱硫、脱氮，另一方面，加氢催化剂需要有大的孔隙，防止原料油中的有机金属化合物和沥青质堵塞催化剂床层的孔隙从而降低催化剂寿命。目前国内外众多石油和石化公司均致力于对现有加氢催化剂进行改进，努力开发出性能更好的加氢催化剂。
常规的加氢催化剂由具有加氢功能的金属或金属氧化物和载体组成，通常是将活性金属化合物的水溶液浸渍于催化剂载体，经干燥和焙烧制得。US2873257和EP0469675公开了负载型催化剂的制备方法，常用的金属组份是包括钴、钼、镍、钨等ⅥB族和Ⅷ族金属，多以氧化铝、硅胶、分子筛、无定型硅酸铝或其混合物为载体。CN102145289A公开了一种通过油滴模板-固相混合法制备大孔载体，进而负载活性组分制备具有丰富的大中孔结构，适合用于多种石油馏分(包括重质油馏分)的催化剂。
由于负载型催化剂存在活性组分分布不均匀，易沉积在载体外表面，高活性组分含量的催化剂需多次浸渍，活性组分易堵塞原有载体孔道等缺点，近年来，非负载型加氢催化剂已越来越成为炼油催化剂开发的一个重要方向。
US4113605公开了一种碳酸镍与三氧化钼生成结晶钼酸镍，随后与氧化铝混合、挤出成型制备加氢催化剂的方法。US6652738和US6534437公开了采用水热法制备混合金属混合物，进而制备不含载体组分的加氢催化剂的方法。CN 101298043公开了一种水热沉积法制备负载型加氢催化剂的方法，以ⅥB族活性金属的盐溶液为前驱体，无机酸溶液为沉淀剂，有机酸为分散剂，在水热条件下通过液相沉积反应生成金属氧化物颗粒，沉积在提前加入的γ-Al2O3上，进而制得催化剂。该法只能制得单金属催化剂，且预先加入γ-Al2O3，使得所得催化剂成型性能难以保证，不适合工业生产。CN103861609公开了Ⅷ族金属化合物和ⅥB族金属化合物的酸性溶液与硅源或铝源的碱性溶液进行沉淀反应制备非负载型加氢催化剂的方法。
现有方法均存在各自的不足：活性组分、载体共混法制备的催化剂易出现分布不均匀的问题；体相型催化剂尽管初始活性高，由于无载体，不利于分子扩散，从而易失活；沉积法易堵塞载体孔道，且成型性能差；活性金属盐与载体前驱体中和法受中和法制备载体方法的限制，所得催化剂孔容、孔径仅比负载型催化剂略有提高，但增幅有限，仍无法满足重质油、渣油等对大孔容、大孔径加氢催化剂的需求。
发明内容
本发明的目的是克服现有制备方法存在的缺陷，提供一种水热法制备油品加氢催化剂的方法。所得催化剂具有比表面大、孔容大、孔径也较大，活性组分与载体配比可根据需要灵活调配，活性组分与载体高度分散，可充分发挥二者的协同作用，成型产品强度好、磨耗低等优点。该方法所得加氢催化剂的大孔结构有利于降低催化过程的传质阻力、提高活性与选择性。
本发明为一种水热合成油品加氢催化剂的方法，其特征在于：
包括如下步骤：
1)将至少一种Ⅷ族非贵金属盐和至少一种ⅥB族金属盐加入至去离子水中，控制Ⅷ族非贵金属与ⅥB族金属摩尔比为0.1～0.8，随后加入有机酸作为分散剂，控制有机酸与ⅥB族金属摩尔比为0.2～2，得到含有活性金属前驱体的酸性溶液；其中有机酸为2～12个碳原子的二元或三元有机羧酸；其中Ⅷ族非贵金属盐选自可溶性镍盐或钴盐中的一种或几种，ⅥB族金属盐选自可溶性钨酸盐或钼酸盐中的一种或几种；
2)适量去离子水中加入尿素与表面活性剂，充分溶解后加入活性氧化铝粉末，混合均匀后进行均质细化处理，得到平均粒度为0.2～12μm的浆料，控制尿素摩尔数为Ⅷ族非贵金属和有机酸总摩尔数的2～10倍，表面活性剂与尿素的质量比为0.1～2；其中所述的表面活性剂选自十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵、十二烷基硫酸钠、十二烷基苯磺酸钠、月桂酸钠、酒石酸钠、聚乙烯醇或聚乙二醇中的一种或几种；其中活性氧化铝为氢氧化铝快速脱水得到的氧化铝粉末；
3)将步骤1)所得溶液和步骤2)所得浆料充分混合后转移至高压反应釜，于120～250℃反应1～24h；
4)反应结束后，将所得浆液固液分离，充分洗涤，干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入稀硝酸捏合为可塑体，挤条成型，干燥、焙烧得到加氢催化剂；其中硝酸的质量浓度为0.5～10％；其中焙烧温度为400～700℃；催化剂中各组分均以氧化物的形式存在，其中氧化铝占催化剂总量的20～75重％，其他金属氧化物总量占催化剂总量的25～80重％。
按照本发明所述的制备方法，其特征在于：
1)将至少一种Ⅷ族非贵金属盐和至少一种ⅥB族金属盐加入至去离子水中，控制Ⅷ族非贵金属与ⅥB族金属摩尔比为0.2～0.5，随后加入有机酸作为分散剂，控制有机酸与ⅥB族金属摩尔比为0.5～1，得到含有活性金属前驱体的酸性溶液；其中有机酸为2～8个碳原子的二元或三元有机羧酸；其中Ⅷ族非贵金属盐选自可溶性镍盐或钴盐中的一种或几种，ⅥB族金属盐选自可溶性钨酸盐或钼酸盐中的一种或几种；
2)适量去离子水中加入尿素与表面活性剂，充分溶解后加入活性氧化铝粉末，混合均匀后进行均质细化处理，得到平均粒度为0.2～5μm的浆料，控制尿素摩尔数为Ⅷ族非贵金属和有机酸总摩尔数的2.5～5倍，表面活性剂与尿素的质量比为0.1～1；其中所述的表面活性剂选自十六烷基三甲基溴化铵、十二烷基苯磺酸钠、酒石酸钠或聚乙二醇中的一种或几种；
3)将步骤1)所得溶液和步骤2)所得浆料充分混合后转移至高压反应釜，于150～220℃反应4～12h；
4)反应结束后，将所得浆液固液分离，充分洗涤，干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入稀硝酸捏合为可塑体，挤条成型，干燥、焙烧得到加氢催化剂；其中硝酸的质量浓度为1.5～5％；其中焙烧温度为500～600℃；催化剂中各组分均以氧化物的形式存在，其中氧化铝占催化剂总量的25～65重％，其他金属氧化物总量占催化剂总量的35～75重％。
本发明与背景技术项目相比，具有的有益效果是：整个制备过程简单，容易控制，适合工业化生产，本发明制备的产品同时具有高比表面、大孔容、大孔径的特点，特别适用于各类重油的催化加氢过程，可满足现代炼油工业对大孔容加氢催化剂的需求，具有广泛的应用前景。
具体实施方式
实施例1
29.1g硝酸镍、70.6g七钼酸铵、28.4g偏钨酸铵依次加入至快速搅拌的640g去离子水中，随后加入48g柠檬酸，于80℃使各金属盐充分溶解，得溶液A。将51g活性氧化铝分批加入快速搅拌的250g去离子水中，随后加入52g尿素，47g十六烷基三甲基溴化铵，进行球磨处理，得到平均粒度0.22μm的浆料B。将溶液A和浆料B充分混合，转移至高压反应釜于150℃反应12h。反应结束后，将所得浆液固液分离，充分洗涤，喷雾干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入3％稀硝酸捏合为可塑体，挤成直径1.5mm圆柱体，室温晾置过夜后于120℃烘干，500℃焙烧得催化剂A1，其BET比表面积为220m2/g，孔容0.48ml/g，平均孔径8.7nm，强度124N/cm。
实施例2
43.6g硝酸镍、53.0g七钼酸铵、56.8g偏钨酸铵依次加入至快速搅拌的720g去离子水中，随后加入67.2g柠檬酸，于80℃使各金属盐充分溶解，得溶液A。将37g活性氧化铝分批加入快速搅拌的200g去离子水中，随后加入132g尿素，13.2g PEG1000，进行球磨处理，得到平均粒度0.45μm的浆料B。将溶液A和浆料B充分混合，转移至高压反应釜于200℃反应8h。反应结束后，将所得浆液固液分离，充分洗涤，喷雾干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入2.5％稀硝酸捏合为可塑体，挤成直径1.5mm圆柱体，室温晾置过夜后于120℃烘干，550℃焙烧得催化剂A2，其BET比表面积为198m2/g，孔容0.42ml/g，平均孔径8.5nm，强度105N/cm。
实施例3
72.8g硝酸镍、61.8g七钼酸铵、42.6g偏钨酸铵依次加入至快速搅拌的800g去离子水中，随后加入91g柠檬酸，于80℃使各金属盐充分溶解，得溶液A。将74g活性氧化铝分批加入快速搅拌的400g去离子水中，随后加入218g尿素，33g酒石酸钠，进行球磨处理，得到平均粒度1.23μm的浆料B。将溶液A和浆料B充分混合，转移至高压反应釜于220℃反应4h。反应结束后，将所得浆液固液分离，充分洗涤，喷雾干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入5％稀硝酸捏合为可塑体，挤成直径1.5mm圆柱体，室温晾置过夜后于120℃烘干，550℃焙烧得催化剂A3，其BET比表面积为225m2/g，孔容0.51ml/g，平均孔径9.1nm，强度137N/cm。
实施例4
43.6g硝酸镍、53.0g七钼酸铵、56.8g偏钨酸铵依次加入至快速搅拌的720g去离子水中，随后加入67g柠檬酸，于80℃使各金属盐充分溶解，得溶液A。将205g活性氧化铝分批加入快速搅拌的1000g去离子水中，随后加入165g尿素，99g十六烷基三甲基溴化铵，进行球磨处理，得到平均粒度1.85μm的浆料B。将溶液A和浆料B充分混合，转移至高压反应釜于200℃反应8h。反应结束后，将所得浆液固液分离，充分洗涤，喷雾干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入3％稀硝酸捏合为可塑体，挤成直径1.5mm圆柱体，室温晾置过夜后于120℃烘干，600℃焙烧得催化剂A4，其BET比表面积为247m2/g，孔容0.59ml/g，平均孔径9.6nm，强度151N/cm。
实施例5
43.6g硝酸镍、44.2g七钼酸铵依次加入至快速搅拌的700g去离子水中，随后加入75g酒石酸，于80℃使各金属盐充分溶解，得溶液A。将166g活性氧化铝分批加入快速搅拌的1000g去离子水中，随后加入420g尿素，42g十六烷基三甲基溴化铵，采用高剪切搅拌器进行均质细化，得到平均粒度12.0μm的浆料B。将溶液A和浆料B充分混合，转移至高压反应釜于250℃反应1h。反应结束后，将所得浆液固液分离，充分洗涤，喷雾干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入3％稀硝酸捏合为可塑体，挤成直径1.5mm圆柱体，室温晾置过夜后于120℃烘干，600℃焙烧得催化剂A5，其BET比表面积为258m2/g，孔容0.53ml/g，平均孔径8.2nm，强度171N/cm。
实施例6
29.1g硝酸镍、88.3g七钼酸铵、142g偏钨酸铵依次加入至快速搅拌的1000g去离子水中，随后加入40g柠檬酸，于80℃使各金属盐充分溶解，得溶液A。将51g活性氧化铝分批加入快速搅拌的350g去离子水中，随后加入49g尿素，98g十六烷基三甲基溴化铵，进行球磨处理，得到平均粒度0.21μm的浆料B。将溶液A和浆料B充分混合，转移至高压反应釜于120℃反应24h。反应结束后，将所得浆液固液分离，充分洗涤，喷雾干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入3％稀硝酸捏合为可塑体，挤成直径1.5mm圆柱体，室温晾置过夜后于120℃烘干，600℃焙烧得催化剂A6，其BET比表面积为211m2/g，孔容0.42ml/g，平均孔径8.0nm，强度115N/cm。
对比例1
将43.6g硝酸镍、53.0g七钼酸铵、56.8g偏钨酸铵依次加入至快速搅拌的175g去离子水中，随后加入67g柠檬酸，于80℃使各金属盐充分溶解，得浸渍液。随后将该浸渍液浸渍于205g商品化的直径1.5mm圆柱形大孔氧化铝载体，室温晾置过夜后于120℃烘干，600℃焙烧得对比催化剂B1，其BET比表面积为208m2/g，孔容0.35ml/g，平均孔径6.7nm，强度85N/cm。
催化剂评价
选取实施例及对比例中制备的催化剂A1～A6和B1在20ml固定床反应装置中进行评价，模型化合物原料组成为：10％萘，5％二苯并噻吩(DBT)(约0.87％硫)，5％喹啉(约0.54％氮)，80％的甲苯，加氢产物经高压分离器(冷高分)和低压分离器分离出液体和气体后，液体产物流入接样罐。
催化剂评价前，在120℃时通入含CS2(2wt％)的环己烷进行预硫化，升温到360℃，硫化10小时，液时空速为2.0h-1。然后降温至340℃，开始进模型化合物原料，控制液时空速为2.0h-1，氢油比300：1，反应压力5.0MPa，反应稳定20小时后取样分析，反应评价结果如表1所示，催化剂A1～A6的评价结果与催化剂B1相比可知，加氢脱硫、加氢脱氮和芳烃加氢活性均显著高于传统方法制备的对比催化剂。
表1 催化剂评价结果
| 催化剂编号 | HDS,％ | HDN,％ | HDAr,％ |
| 催化剂A1 | 99.3 | 91.2 | 57.2 |
| 催化剂A2 | 99.7 | 92.5 | 60.1 |
| 催化剂A3 | 99.1 | 91.5 | 56.2 |
| 催化剂A4 | 98.5 | 90.7 | 53.5 |
| 催化剂A5 | 96.1 | 83.1 | 47.3 |
| 催化剂A6 | 97.3 | 86.2 | 48.8 |
| 催化剂B1 | 94.1 | 71.2 | 42.2 |
Claims (2)
1.一种水热合成加氢催化剂的方法，其特征在于，按以下步骤进行：
1)将至少一种Ⅷ族非贵金属盐和至少一种ⅥB族金属盐加入至去离子水中，控制Ⅷ族非贵金属与ⅥB族金属摩尔比为0.1～0.8，随后加入有机酸作为分散剂，控制有机酸与ⅥB族金属摩尔比为0.2～2，得到含有活性金属前驱体的酸性溶液；其中有机酸为2～12个碳原子的二元或三元有机羧酸；其中Ⅷ族非贵金属盐选自可溶性镍盐或钴盐中的一种或几种，ⅥB族金属盐选自可溶性钨酸盐或钼酸盐中的一种或几种；
2)适量去离子水中加入尿素与表面活性剂，充分溶解后加入活性氧化铝粉末，混合均匀后进行均质细化处理，得到平均粒度为0.2～12μm的浆料，控制尿素摩尔数为Ⅷ族非贵金属和有机酸总摩尔数的2～10倍，表面活性剂与尿素的质量比为0.1～2；其中所述的表面活性剂选自十二烷基三甲基溴化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵、十二烷基硫酸钠、十二烷基苯磺酸钠、月桂酸钠、酒石酸钠、聚乙烯醇或聚乙二醇中的一种或几种；其中活性氧化铝为氢氧化铝快速脱水得到的氧化铝粉末；
3)将步骤1)所得溶液和步骤2)所得浆料充分混合后转移至高压反应釜，于120～250℃反应1～24h；
4)反应结束后，将所得反应产物固液分离，充分洗涤，干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入稀硝酸捏合为可塑体，挤条成型，干燥、焙烧得到加氢催化剂；其中硝酸的质量浓度为0.5～10％；其中焙烧温度为400～700℃；催化剂中各组分均以氧化物的形式存在，其中氧化铝占催化剂总量的20～75wt％，其他金属氧化物总量占催化剂总量的25～80wt％。
2.根据权利要求1所述的方法，其特征在于：
1)将至少一种Ⅷ族非贵金属盐和至少一种ⅥB族金属盐加入至去离子水中，控制Ⅷ族非贵金属与ⅥB族金属摩尔比为0.2～0.5，随后加入有机酸作为分散剂，控制有机酸与ⅥB族金属摩尔比为0.5～1，得到含有活性金属前驱体的酸性溶液；其中有机酸为2～8个碳原子的二元或三元有机羧酸；其中Ⅷ族非贵金属盐选自可溶性镍盐或钴盐中的一种或几种，ⅥB族金属盐选自可溶性钨酸盐或钼酸盐中的一种或几种；
2)适量去离子水中加入尿素与表面活性剂，充分溶解后加入活性氧化铝粉末，混合均匀后进行均质细化处理，得到平均粒度为0.2～2μm的浆料，控制尿素摩尔数为Ⅷ族非贵金属和有机酸总摩尔数的2.5～5倍，表面活性剂与尿素的质量比为0.1～1；其中所述的表面活性剂选自十六烷基三甲基溴化铵、十二烷基苯磺酸钠、酒石酸钠或聚乙二醇中的一种或几种；
3)将步骤1)所得溶液和步骤2)所得浆料充分混合后转移至高压反应釜，于150～220℃反应4～12h；
4)反应结束后，将所得浆液固液分离，充分洗涤，干燥得到活性组分前驱体与载体前驱体的混合粉末，随后加入稀硝酸捏合为可塑体，挤条成型，干燥、焙烧得到加氢催化剂；其中硝酸的质量浓度为1.5～5％；其中焙烧温度为500～600℃；催化剂中各组分均以氧化物的形式存在，其中氧化铝占催化剂总量的25～65wt％，其他金属氧化物总量占催化剂总量的35～75wt％。
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