CN116139884A - 一种硫化型加氢催化剂的制备方法 - Google Patents
一种硫化型加氢催化剂的制备方法 Download PDFInfo
- Publication number
- CN116139884A CN116139884A CN202211716208.4A CN202211716208A CN116139884A CN 116139884 A CN116139884 A CN 116139884A CN 202211716208 A CN202211716208 A CN 202211716208A CN 116139884 A CN116139884 A CN 116139884A
- Authority
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- China
- Prior art keywords
- hydrogenation catalyst
- microwave drying
- preparing
- ammonium
- sulfided
- Prior art date
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- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000005855 radiation Effects 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 238000004898 kneading Methods 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000004537 pulping Methods 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- YNNGZCVDIREDDK-UHFFFAOYSA-N aminocarbamodithioic acid Chemical compound NNC(S)=S YNNGZCVDIREDDK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- -1 hydrocarbyl sulfate Chemical class 0.000 claims description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000012028 Fenton's reagent Substances 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 claims description 2
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical class CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000001913 cellulose Chemical class 0.000 claims description 2
- 229920002678 cellulose Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229940058352 levulinate Drugs 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical class CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000768 polyamine Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 7
- 238000004073 vulcanization Methods 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- DCYNAHFAQKMWDW-UHFFFAOYSA-N azane;carbamodithioic acid Chemical compound N.NC(S)=S DCYNAHFAQKMWDW-UHFFFAOYSA-N 0.000 description 5
- 238000011066 ex-situ storage Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 150000008116 organic polysulfides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical class [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000010981 methylcellulose Nutrition 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229930192474 thiophene Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明公开了一种硫化型加氢催化剂的制备方法。该方法包括:先将二硫代氨基甲酸铵、镍盐和/或钴盐和一定量的去离子水混合加热搅拌,然后加入四硫代钼酸铵和/或四硫代钨酸铵,将得到的含硫复合活性金属前驱体浸渍液于50℃~90℃温度下与拟薄水铝石粉(干基60~70wt%)、拟薄水铝石滤饼(干基20~25wt%)、粘合剂、微波敏化剂和分散剂混合,然后超声分散、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,再用辐射频率为2450MHz的微波干燥得到硫化型加氢催化剂。本发明方法高效简便、活性金属分散均匀,不同活性金属之间协同性好,活性金属的有效利用率高,制备得到的硫化型加氢催化剂具有优异的加氢性能。
Description
技术领域
本发明涉及一种硫化型加氢催化剂的制备方法。
背景技术
石油馏分加氢工艺是目前生产清洁油品的关键技术,其中,高性能的加氢催化剂是加氢技术的关键。
传统的石油馏分加氢催化剂是将钴、镍、钨和钼等活性组份负载在多孔载体材料上,制备成为负载型固体催化剂。其中,钴、镍、钨和钼等活性组份以氧化物形式存在,而实际使用时,要使用硫化剂将石油馏分加氢催化剂上活性组份转变成为钴、镍、钨和钼的硫化物形式,才能获得理想的加氢活性和稳定性。因此,石油馏分加氢催化剂在使用前需要经过硫化。
加氢催化剂硫化方法分为两种:器内硫化法和器外硫化法。器内硫化法是将氧化态催化剂装入加氢反应器内,在升温过程中向反应器中通入氢气和硫化剂进行预硫化,这一方法的缺点是:需专门的预硫化设备,硫化时间长,硫化成本高,硫化剂毒性大、易燃,容易对人、对环境造成污染。
器外硫化法是将催化剂地预硫化转移至专门的硫化反应装置上进行或制成的催化剂已是硫化态的催化剂,从而使催化剂装入加氢反应器中即可使用,无须再硫化,成为近年来加氢催化剂制备技术的发展趋势。目前,工业应用较多的加氢催化剂器外硫化技术主要由两种技术路线:
(1)第一种技术路线是在专门的预硫化装置上,在氢气和硫化氢或易分解的有机硫化剂的存在下完成催化剂的预硫化,然后经含氧气体钝化处理制成不自燃的预硫化型加氢催化剂;
(2)第二种技术路线是先将硫化剂(由含烯烃组分的石油溶剂、元素硫、植物油、有机硫化物、有机多硫化物、砜、亚砜和硫化促进剂等组分)采用升华、熔融或浸渍的方法引入到氧化态的加氢催化剂的空隙中,然后在氮气存在下经升温处理使催化剂部分预硫化,最后将催化剂装入加氢反应器中,在开工升温过程中和氢气的存在下完成催化剂的预硫化。
美国专利US5958816中提出采用硫化床工艺,在专用的预硫化反应器中用H2/H2S气体硫化加氢催化剂,然后用含氧气体或空气钝化,使用时装入反应器直接开工,该专利解决了硫化过程飞温和酸性水释放问题,但工艺流程复杂、加工成本高,空气钝化过程中有硫酸根生成,并残留在催化剂上,影响催化剂的使用寿命。
中国专利申请91101805.7公开了一种将硫掺入烃处理催化剂的孔中的方法,其特点为:先采用溶剂稀释的硫化剂处理催化剂,然后在水蒸气存在下,在高于250℃的温度下硫化处理。所用的硫化剂由元素硫和在氢气存在下易分解出硫化氢的有机硫化合物组成,所用的溶剂为含有烯烃馏分或植物油的溶剂油。中国专利申请85107953公开了一种处理加氢催化剂的方法,其中主要包含先用石油溶剂溶解和稀释的元素硫、多种有机多硫化物在50~150℃浸渍处理加氢催化剂,然后在无氢气的气氛中在低于275℃下处理,将活性金属氧化物进行硫化,最后在氢气的存在下在高于275℃的温度下进行活化。美国专利US6365542公开了一种加氢催化剂器外预硫化的方法,其特点是先用含元素硫和烯烃的油在100~300℃的温度下经过氮气处理。
美国专利US5985787公开了一种加氢催化剂的预硫化方法,其特点是硫化剂采用溶剂稀释的含烯烃的油、植物油、有机硫化物、有机多硫化物、元素硫等,其中既要有分解温度低于220℃的硫化物,也要有分解温度高于220℃的硫化物。美国专利US5681782中对过去的催化剂预硫化技术进行了改进,在添加硫化物的过程中加入了一种含氧有机化合物。中国专利申请98801896.9公开了一种加氢催化剂器外硫化的硫化剂,该硫化剂以C4~C16的叔硫醇为主剂,与H2S、CS2、伯或仲硫醇、有机多硫化物、噻吩及其衍生物、亚砜、砜、环丁砜等配合使用。中国专利申请00100400.X公开了一种加氢催化剂的器外预硫化方法,其特点是先将含烯烃的组份、元素硫和助剂混合,在100~220℃加热0.5小时以上,然后用得到的产物浸渍催化剂,并在100~300℃的温度下经过氮气处理1小时以上。
以上报道的专利技术均是器外预硫化技术,与器内硫化相比,具有催化剂活性高,节约开工时间,简化开工步骤,对人和环境污染小等优点。但器外预硫化与器内预硫化一样,预硫化过程在氢气作用下进行,氧化态催化剂可能出现氢解反应,而且活性组分与载体结合力往往太强,使的加氢催化剂不能被完全硫化,导致催化剂的活性不能进一步提高。催化剂经过氧化态再预硫化使用,使催化剂的生产步骤增加,生产成本加大,直接影响工艺的经济性。
此外,近年来报道了另一种硫化型加氢催化剂的新型制备方法,即采用Mo或W的硫化物前驱体直接制备硫化型加氢催化剂。中国专利CN1569331公开了一种改性钴钼基硫化物催化剂及其制备方法,通过配制硫代钼酸铵溶液,共沉淀钼、钴和第三种过渡金属组元,在氮气保护下焙烧,制得黑色粉末状催化剂。该方法的缺点是只能制备粉末状催化剂,不能用于大规模的固定床加氢装置;制备过程有废液产生,存在环保问题,制备成本高。
中国专利CN200410039449.5公开了采用可溶性硫代钼酸盐和硫代钨酸盐溶液将第IVB族金属Mo和W的前驱体引入到加氢催化剂载体的空隙中,并在氮气中经加热处理转化为Mo和W的硫化物,然后再引入Co或Ni的可溶性盐溶液,并在氮气中经加热处理转化为Co或Ni的硫化物,从而制得负载有金属硫化物的硫化型加氢催化剂。中国专利CN200810228363.5采用浸渍溶液浸渍需要的催化剂载体,然后经干燥和热处理即得硫化型加氢催化剂,其特征在于所述的浸渍溶液含有金属Mo或W的硫化物前驱体,同时含有Ni或Co无机盐的络合物;所述的热处理过程为在200~350℃下处理1~10小时;干燥和热处理不需氮气保护。
发明内容
本发明的目的就在于克服上述现有技术的不足之处,通过引入多功能络合剂,结合热浸渍含微波敏化剂的氧化铝载体,超声处理和微波干燥,促使催化剂更易生成活性高的金属硫化物活性相,从而使硫化型加氢催化剂具有优异的加氢性能。
本发明一种硫化型加氢催化剂的制备方法,所述制备方法包括:先将二硫代氨基甲酸铵、镍盐和/或钴盐和一定量的去离子水混合加热搅拌,然后加入四硫代钼酸铵和/或四硫代钨酸铵,将得到的含硫复合活性金属前驱体浸渍液于50℃~90℃温度下与拟薄水铝石粉(干基60~70wt%)、拟薄水铝石滤饼(干基20~25wt%)、粘合剂、微波敏化剂和分散剂混合,然后超声分散、打浆、混捏、挤条成型,然后在氮气保护下,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为100℃~120℃,再用辐射频率为2450MHz的微波干燥,微波干燥温度为350℃~600℃,干燥后得到硫化型加氢催化剂;所述的二硫代氨基甲酸铵使用的摩尔量为镍盐和/或钴盐摩尔量的50%~300%,优选100%~150%。
本发明上述硫化型加氢催化剂的制备方法中,优选所述的镍盐和/或钴盐选自碱式碳酸盐、硝酸盐和醋酸盐等中的一种或多种,优选碱式碳酸盐。
本发明上述硫化型加氢催化剂的制备方法中,优选所述的粘结剂为铝溶胶、硅溶胶、硅酸铝和硅铝凝胶等中的一种或多种。
本发明上述硫化型加氢催化剂的制备方法中,优选所述的微波敏化剂为芬顿试剂、活性炭、石墨、导电碳黑、半导电碳黑和碳纤维敏化剂等中的一种或多种。
本发明上述硫化型加氢催化剂的制备方法中,优选所述的分散剂为烷基酰胺类化合物、多聚羧酸、多聚羧酸与多元胺组成的低聚物、三乙基己基磷酸、烃基硫酸盐、烃基磺酸盐、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯、硅酸盐、聚乙烯蜡、氧化聚乙烯蜡、聚乙二醇、聚乙烯醇、聚丙烯醇、甲基纤维素、羧甲基纤维素、异丙醇、仲丁醇、乙酰丙酸酯、水解聚马来酸酐(HPMA)、乙烯-丙烯酸共聚物、乙烯-醋酸乙烯共聚物、高级脂肪酸的金属盐、脂肪酸类化合物、脂肪族酰胺类化合物、酯类化合物、石蜡、聚氨酯、脂肪酸甘油酯,脂肪酸山梨坦、吐温、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚和丙烯酸类聚合物(如LBD-1分散剂)等中的一种或多种,用量为载体组分重量的1wt%~20wt%。
本发明上述硫化型加氢催化剂的制备方法中,优选所述的超声时间为5~30分钟。
本发明上述硫化型加氢催化剂的制备方法中,优选所述的840MHz的微波干燥时间为10~30分钟;2450MHz的微波干燥时间为20~120分钟。
本发明上述硫化型加氢催化剂的制备方法中,优选所述的硫化型加氢催化剂以最终催化剂的重量为基准,钼和/或钨以元素计的含量为5wt%~30wt%,钴和/或镍以元素计的含量为1wt%~10wt%。
本发明还进一步提供了上述制备方法制得的硫化型加氢催化剂。
本发明方法高效简便、活性金属分散均匀,不同活性金属之间协同性好,活性金属的有效利用率高,通过引入多功能络合剂,结合热浸渍、超声处理,在氮气保护下,先用辐射频率为840MHz的微波干燥,再用辐射频率为2450MHz的微波干燥,促使催化剂更易生成活性高的金属硫化物活性相,从而使硫化型加氢催化剂具有优异的加氢性能。本发明方法制得的硫化型加氢催化剂主要用于加氢精制过程,适合于处理焦化汽柴油、催化裂化汽柴油、减压瓦斯油、热精制瓦斯油、催化精制瓦斯油、催化精制循环油、焦化瓦斯油、脱沥青油等各种油品中的一种或多种,原料通常为含沸点180~700℃的烃类。
具体实施方式
下面用具体实施例来详细说明本发明的技术特点,但实施例并不限制本发明的保护范围。
本发明硫化型加氢催化剂的制备方法,主要包括制备步骤如下:先将二硫代氨基甲酸铵、镍盐和/或钴盐和一定量的去离子水混合加热搅拌,然后加入四硫代钼酸铵和/或四硫代钨酸铵,将得到的含硫复合活性金属前驱体浸渍液于50℃~90℃温度下与拟薄水铝石粉(干基60~70wt%)、拟薄水铝石滤饼(干基20~25wt%)、粘合剂、微波敏化剂和分散剂混合,然后超声分散、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为100℃~120℃,再用辐射频率为2450MHz的微波干燥,微波干燥温度为350℃~600℃,干燥后得到硫化型加氢催化剂。具体实施例操作如下:
实施例1:
将13克的二硫代氨基甲酸铵、6克的碱式碳酸镍、6克的柠檬酸和40克的去离子水混合,于90℃加热搅拌,然后加入30克四硫代钼酸铵,将得到的含硫复合活性金属前驱体浸渍液于90℃温度下与100克拟薄水铝石粉(干基60wt%)、50克拟薄水铝石滤饼(干基25wt%)、10g铝溶胶(固含量质量分数为35%)、1克活性炭和1克羧甲基纤维素混合,然后超声分散5分钟、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为100℃,干燥时间为10分钟,再用辐射频率为2450MHz的微波干燥,微波干燥温度为600℃,干燥时间为20分钟,得到一种硫化型加氢催化剂1。
实施例2:
将2.5克二硫代氨基甲酸铵、6克硝酸镍、3克醋酸镍、6克乙二醇和40克的去离子水混合,于50℃加热搅拌,然后加入30克四硫代钨酸铵,将得到的含硫复合活性金属前驱体浸渍液于50℃温度下与80克拟薄水铝石粉(干基65wt%)、90克拟薄水铝石滤饼(干基23wt%)、15g硅溶胶(固含量质量分数为35%)、0.5克芬顿试剂和0.5克聚乙二醇混合,然后超声分散30分钟、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为120℃,干燥时间为30分钟,再用辐射频率为2450MHz的微波干燥,微波干燥温度为350℃,干燥时间为100分钟,得到一种硫化型加氢催化剂2。
实施例3:
将4.5克二硫代氨基甲酸铵、4.5克硝酸镍、3.8克醋酸镍、6克乙二胺四乙酸和40克的去离子水混合,于60℃加热搅拌,然后加入20克四硫代钼酸铵和10克四硫代钨酸铵,将得到的含硫复合活性金属前驱体浸渍液于60℃温度下80克拟薄水铝石粉(干基68wt%)、100克拟薄水铝石滤饼(干基20wt%)、8g硅溶胶(固含量质量分数为35%)和8g铝溶胶(固含量质量分数为35%)、0.5克石墨和0.5克吐温混合,然后超声分散25分钟、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为110℃,干燥时间为20分钟,再用辐射频率为2450MHz的微波干燥,微波干燥温度为400℃,干燥时间为60分钟,得到一种硫化型加氢催化剂3。
实施例4:
将4.5克二硫代氨基甲酸铵、8.4克醋酸镍、5克乙醇胺和一定量的去离子水混合,于70℃加热搅拌,然后加入10克四硫代钼酸铵和20克四硫代钨酸铵,将得到的含硫复合活性金属前驱体浸渍液于70℃温度下80克拟薄水铝石粉(干基70wt%)、100克拟薄水铝石滤饼(干基22wt%)、12g硅酸铝(固含量质量分数为35%)、0.5克半导电碳黑和0.5克古尔胶混合,然后超声分散15分钟、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为120℃,干燥时间为12分钟,再用辐射频率为2450MHz的微波干燥,微波干燥温度为450℃,干燥时间为45分钟,得到一种硫化型加氢催化剂4。
实施例5:
将6克二硫代氨基甲酸铵、6克硝酸镍、3克硝酸钴、4克柠檬酸和40克去离子水混合,于80℃加热搅拌10分钟,然后加入30克四硫代钼酸铵,将得到的含硫复合活性金属前驱体浸渍液于80℃温度下与90克拟薄水铝石粉(干基65wt%)、80克拟薄水铝石滤饼(干基21wt%)、10g硅铝凝胶(固含量质量分数为35%)、0.5克碳纤维敏化剂和0.5克仲丁醇混合,然后超声分散10分钟、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为100℃,干燥时间为10分钟,再微波辐射频率为2450MHz,微波干燥温度为500℃,干燥时间为30分钟,得到一种硫化型加氢催化剂5。
对比例1:
将6克硝酸镍、3克硝酸钴、4克柠檬酸和40克去离子水混合,于30℃下搅拌1小时,然后加入30克四硫代钼酸铵,将得到的含硫复合活性金属前驱体浸渍液用去离子水定容,于30℃温度下等体积浸渍在100克的氧化铝载体上,静置养生4小时,在氮气保护下,于500℃烘箱中干燥5小时,得到加氢催化剂A。
催化剂活性评价条件为:以催化裂化柴油为原料油(表1),反应压力为8.0MPa、氢油体积比为500:1、体积空速为3.0h-1、反应温度为340℃。
表1原料油主要性质
项目 | 数据 |
密度(20℃),g/cm3 | 0.8832 |
馏程,℃ | 168~372 |
S,μg/g | 9637 |
N,μg/g | 825 |
表2催化剂样品的活性以相对加氢脱硫率表示(以对比例加氢催化剂A为100)
催化剂编号 | 1 | 2 | 3 | 4 | 5 | A |
相对加氢脱硫率 | 142 | 139 | 136 | 145 | 127 | 100 |
相对加氢脱氮率 | 137 | 135 | 132 | 139 | 124 | 100 |
从以上结果可以看出,本发明方法得到的硫化型加氢催化剂具有更好的加氢性能。
Claims (10)
1.一种硫化型加氢催化剂的制备方法,其特征在于,所述制备方法包括:先将二硫代氨基甲酸铵、镍盐和/或钴盐和一定量的去离子水混合加热搅拌,然后加入四硫代钼酸铵和/或四硫代钨酸铵,将得到的含硫复合活性金属前驱体浸渍液于50℃~90℃温度下与干基60~70wt%的拟薄水铝石粉、干基20~25wt%的拟薄水铝石滤饼、粘合剂、微波敏化剂和分散剂混合,然后超声分散、打浆、混捏、挤条成型,然后在氮气保护下,先用辐射频率为840MHz的微波干燥,微波干燥温度为100℃~120℃,再用辐射频率为2450MHz的微波干燥,微波干燥温度为350℃~600℃,干燥后得到硫化型加氢催化剂;所述的二硫代氨基甲酸铵使用的摩尔量为镍盐和/或钴盐摩尔量的50%~300%。
2.根据权利要求1所述的硫化型加氢催化剂的制备方法,其特征在于,所述的二硫代氨基甲酸铵使用的摩尔量为镍盐和/或钴盐摩尔量的100%~150%。
3.根据权利要求1所述的硫化型加氢催化剂的制备方法,其特征在于,所述的镍盐和/或钴盐选自碱式碳酸盐、硝酸盐和醋酸盐中的一种或多种。
4.根据权利要求1所述的硫化型加氢催化剂的制备方法,其特征在于,所述的粘结剂为铝溶胶、硅溶胶、硅酸铝和硅铝凝胶中的一种或多种。
5.根据权利要求1所述的硫化型体相加氢催化剂的制备方法,其特征在于,所述的微波敏化剂为芬顿试剂、活性炭、石墨、导电碳黑、半导电碳黑和碳纤维敏化剂中的一种或多种。
6.根据权利要求1所述的硫化型加氢催化剂的制备方法,其特征在于,所述的分散剂为烷基酰胺类化合物、多聚羧酸、多聚羧酸与多元胺组成的低聚物、三乙基己基磷酸、烃基硫酸盐、烃基磺酸盐、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯、硅酸盐、聚乙烯蜡、氧化聚乙烯蜡、聚乙二醇、聚乙烯醇、聚丙烯醇、甲基纤维素、羧甲基纤维素、异丙醇、仲丁醇、乙酰丙酸酯、水解聚马来酸酐(HPMA)、乙烯-丙烯酸共聚物、乙烯-醋酸乙烯共聚物、高级脂肪酸的金属盐、脂肪酸类化合物、脂肪族酰胺类化合物、酯类化合物、石蜡、聚氨酯、脂肪酸甘油酯,脂肪酸山梨坦、吐温、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚和丙烯酸类聚合物中的一种或多种,用量为载体组分重量的1wt%~20wt%。
7.根据权利要求1所述的硫化型加氢催化剂的制备方法,其特征在于,所述的超声时间为5~30分钟。
8.根据权利要求1所述的硫化型加氢催化剂的制备方法,其特征在于,所述的840MHz的微波干燥时间为10~30分钟;2450MHz的微波干燥时间为20~120分钟。
9.根据权利要求1所述的硫化型加氢催化剂的制备方法,其特征在于,所述的硫化型加氢催化剂以最终催化剂的重量为基准,钼和/或钨以元素计的含量为5wt%~30wt%,钴和/或镍以元素计的含量为1wt%~10wt%。
10.一种权利要求1~9所述的制备方法制备得到的硫化型加氢催化剂。
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