CN113559890A - Hydrogenation catalyst and preparation method and application thereof - Google Patents
Hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN113559890A CN113559890A CN202010352288.4A CN202010352288A CN113559890A CN 113559890 A CN113559890 A CN 113559890A CN 202010352288 A CN202010352288 A CN 202010352288A CN 113559890 A CN113559890 A CN 113559890A
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- metal component
- hydrogenation
- hydrogenation catalyst
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 171
- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 124
- 239000002184 metal Substances 0.000 claims abstract description 124
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 45
- 239000011574 phosphorus Substances 0.000 claims abstract description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 6
- 238000002835 absorbance Methods 0.000 claims abstract description 4
- 238000000727 reflectance ultraviolet--visible spectrophotometry Methods 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 44
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- 239000011593 sulfur Substances 0.000 claims description 43
- 230000004913 activation Effects 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 27
- -1 hydroxycarbonates Chemical class 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 19
- 230000003213 activating effect Effects 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000295 fuel oil Substances 0.000 claims description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 230000008093 supporting effect Effects 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 30
- 229910052596 spinel Inorganic materials 0.000 abstract description 14
- 239000011029 spinel Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005470 impregnation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000006259 organic additive Substances 0.000 description 10
- 150000002736 metal compounds Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
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- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
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- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J23/005—Spinels
-
- 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
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
本发明涉及加氢催化剂制备领域，公开了一种加氢催化剂，该催化剂包括载体和负载在所述载体上的加氢活性金属组分，所述加氢活性金属组分含有至少一种VIB族金属组分以及至少一种VIII族金属组分，所述载体为含磷氧化铝；该加氢催化剂经漫反射紫外可见光谱(DRUVS)测量时，630nm与500nm处的吸光度分别为F630和F500，且二者的比值Q＝F630/F500为1.3‑3；所述载体中还含有硫元素，以载体的总量为基准，硫元素的含量为0.7‑3重量％。本发明提供的加氢催化剂具有特定的尖晶石结构Ni(Co)Al2O4，所述加氢催化剂具有更好的加氢活性和更高的稳定性。The invention relates to the field of hydrogenation catalyst preparation, and discloses a hydrogenation catalyst. The catalyst comprises a carrier and a hydrogenation active metal component supported on the carrier, wherein the hydrogenation active metal component contains at least one VIB group A metal component and at least one Group VIII metal component, the carrier is phosphorus-containing alumina; when the hydrogenation catalyst is measured by diffuse reflectance ultraviolet-visible spectroscopy (DRUVS), the absorbances at 630nm and 500nm are F 630 and F, respectively 500 , and the ratio Q=F 630 /F 500 of the two is 1.3-3; the carrier also contains elemental sulfur, and the content of elemental sulfur is 0.7-3 wt % based on the total amount of the carrier. The hydrogenation catalyst provided by the present invention has a specific spinel structure Ni(Co)Al 2 O 4 , and the hydrogenation catalyst has better hydrogenation activity and higher stability.
Description
Technical Field
The invention relates to the field of hydrogenation catalyst preparation, and particularly relates to a hydrogenation catalyst, and a preparation method and application thereof.
Background
For heavy raw oil, after being pretreated by a hydrogenation process, secondary processing is carried out, so that the yield of light oil can be improved, and the content of pollutants such as sulfur, nitrogen and the like in the oil can be reduced, therefore, the demand of the market on the light oil is continuously increased, and the environmental protection regulations tend to be strict today, and the heavy raw oil is generally favored by oil refining manufacturers. Compared with light oil products, heavy oil contains a large amount of impurities such as sulfur, nitrogen, metal and the like, and contains easily coking species such as asphaltene and the like, so that the heavy oil has higher requirements on the activity and the stability of the catalyst. The deactivation of the heavy oil hydrogenation catalyst is caused by two factors, namely, the deposition of metal to destroy the original active phase structure of the catalyst, and carbon deposits on the surface of the active phase to cover the active center, so that the reaction performance of the catalyst is reduced. Therefore, how to improve the stability of the active phase structure of the catalyst and reduce the damage, aggregation and poisoning of the active phase structure of the catalyst in the reaction process is a key technology for improving the activity stability of the catalyst.
CN107583659A discloses a gasoline selective hydrodesulfurization catalyst, wherein a composite alumina carrier containing zinc aluminate spinel is prepared by a non-constant pH alternative titration method, and the catalyst prepared by loading cobalt and molybdenum has good selectivity and reaction stability in the gasoline hydrodesulfurization process.
Compared with distillate oil, the heavy oil hydrogenation catalyst needs higher reaction activity and has higher requirement on activity stability, and the prior art which is not disclosed can well meet the requirements of both the activity and the stability of the catalyst, thereby seriously influencing the actual industrial application effect of the catalyst.
Disclosure of Invention
The invention aims to overcome the defects that the preparation process of the catalyst is complicated and the activity and the stability of the catalyst need to be further improved in the prior art, and provides a hydrogenation catalyst, a preparation method and application thereof.
The inventor of the invention finds that in the process of preparation of the hydrogenation catalyst, pseudo-boehmite, a phosphorus-containing compound and a sulfur-containing compound are mixed and then activated under specific conditions, so that Ni (Co) Al with a specific spinel structure and containing phosphorus and sulfur in a carrier can be obtained2O4The hydrogenation catalyst has better hydrogenation activity and higher stability.
In addition, the inventor of the present invention also finds that, in the preparation process of the hydrogenation catalyst, the pseudo-boehmite, the phosphorus-containing compound and the sulfur-containing compound are directly mixed with the precursor of the hydrogenation active metal component, and the mixture is formed, and then is dried and roasted once to obtain the hydrogenation catalyst. Compared with the prior art, the method omits the process of drying and roasting the pseudo-boehmite to prepare the carrier, simplifies the preparation process, and ensures that the prepared hydrogenation catalyst has a specific spinel structure Ni (Co) Al after being treated at a specific activation temperature2O4The hydrogenation catalyst also has better hydrogenation activity and higher stability.
In order to achieve the above object, the first aspect of the present invention provides a hydrogenation catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component comprises at least one group VIB metal component and at least one group VIII metal component, and the carrier is phosphorus-containing alumina;
when the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS), the absorbances at 630nm and 500nm are respectively F630And F500And the ratio Q ═ F of the two630/F5001.3 to 3;
the carrier also contains sulfur element, and the content of the sulfur element is 0.7-3 wt% based on the total amount of the carrier.
Preferably, Q is 1.4-2.5.
In a second aspect, the present invention provides a method for preparing a hydrogenation catalyst, comprising the steps of:
(1) mixing pseudo-boehmite with a phosphorus-containing compound and a sulfur-containing compound, and then molding, drying and optionally roasting to obtain a molded object;
(2) loading a hydrogenation active metal component on the formed object, and then optionally drying;
(3) activating the solid product obtained in the step (2), wherein the activating conditions comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours;
the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.
In a third aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:
mixing and molding pseudo-boehmite, a phosphorus-containing compound, a sulfur-containing compound and a precursor of a hydrogenation active metal component, and then sequentially drying and activating to obtain a hydrogenation catalyst; the conditions for the activation include: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours;
the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.
Preferably, the temperature of the activation is 610-780 ℃, more preferably 630-750 ℃, and most preferably 650-730 ℃.
Preferably, the temperature rise rate of the activation is 50-600 deg.C/hr, preferably 100-550 deg.C/hr.
In a fourth aspect, the present invention provides a hydrogenation catalyst prepared by the above method.
The hydrogenation catalyst prepared by the method has better activity and higher stability, and is particularly suitable for heavy oil hydrogenation reaction, so the fifth aspect of the invention provides the application of the hydrogenation catalyst in the heavy oil hydrogenation reaction.
Through the technical scheme, the preparation process of the method is simple, and the cost of the catalyst is reduced; after being treated by specific activation temperature, the hydrogenation catalyst provided by the invention has specific spinel structure Ni (Co) Al2O4The hydrogenation catalyst has better hydrogenation activity and higher stability, thereby improving the operation period of the catalyst and being beneficial to improving the economic benefit of a refinery.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a hydrogenation catalyst, which comprises a carrier and hydrogenation active metal components loaded on the carrier, wherein the hydrogenation active metal components comprise at least one VIB group metal component and at least one VIII group metal component, and the carrier is phosphorus-containing alumina;
when the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS), the absorbances at 630nm and 500nm are respectively F630And F500And the ratio Q ═ F of the two630/F5001.3 to 3;
the carrier also contains sulfur element, and the content of the sulfur element is 0.7-3 wt% based on the total amount of the carrier.
The inventor of the invention finds that although the initial activity of the catalyst is influenced by the formation of the spinel structure, the formation of a proper amount of the spinel structure does not bring too much influence on the total activity of the catalyst, and the formed spinel structure gradually releases the reaction activity along with the extension of the catalyst participating in the reaction process, so that the activity stability of the catalyst is better, the service life of the catalyst is greatly prolonged on the premise of meeting the basic activity requirement, and the production efficiency is improved.
According to a preferred embodiment of the invention, Q is between 1.4 and 2.5. The inventor of the present invention further found that when a specific hydrogenation active metal component is supported on an alumina carrier containing phosphorus and sulfur, and the above ratio Q representing the content of the spinel structure in the catalyst is 1.4 to 2.5, the catalyst is favorable for obtaining better initial activity, and further improving subsequent hydrogenation activity and stability. When the Q value is less than 1, the improvement of the activity stability is not obvious; when the Q value is more than 3, the initial activity is too low, which affects the normal use of the catalyst.
According to the invention, the content of elemental sulphur is preferably 0.9 to 2.5 wt.%, based on the total amount of support. In this preferred case, the hydrogenation catalyst is more active and more stable.
According to the invention, the phosphorus content is preferably from 0.5 to 8% by weight, preferably from 1 to 6% by weight, calculated as oxide, based on the total amount of support. In this preferred case, the hydrogenation catalyst is more active and more stable.
According to the present invention, the group VIB metal component may be selected from at least one of chromium, molybdenum and tungsten, and the group VIII metal component may be selected from at least one of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, so long as it is advantageous to improve the hydrogenation activity and stability of the hydrogenation catalyst. Preferably, the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.
The invention has wide selectable range of the dosage of the VIB group metal component and the VIII group metal component, and preferably, the total amount of the hydrogenation catalyst is taken as a reference, the content of the carrier is 30-99 wt%, the content of the VIB group metal component is 0.5-50 wt% and the content of the VIII group metal component is 0.5-20 wt% calculated by oxides.
Further preferably, the content of the carrier is 40-94 wt%, the content of the VIB group metal component is 5-45 wt% and the content of the VIII group metal component is 1-15 wt% calculated by oxide based on the total amount of the hydrogenation catalyst.
The hydrogenation catalyst provided by the invention can also contain any auxiliary agent which does not affect the performance of the hydrogenation catalyst or can improve the performance of the hydrogenation catalyst, such as at least one of elements in groups IA, IIA, IIIA, IVA, VA, VIIA, IIB and IIIB and rare earth metal elements, preferably at least one of boron, fluorine, silicon, sodium, magnesium, lithium, zinc, calcium, potassium, titanium, lanthanum and cerium, and the content of the auxiliary agent calculated by simple substance elements is not more than 10 wt%, preferably 0.5-6 wt% based on the catalyst.
Compared with the hydrogenation catalyst provided by the prior art, the hydrogenation catalyst provided by the invention has better hydrogenation activity and reaction stability. The hydrogenation catalyst provided by the invention can be used alone or combined with other catalysts when used for hydrogenation reaction of hydrocarbon oil.
In a second aspect, the present invention provides a method for preparing a hydrogenation catalyst, comprising the steps of:
(1) mixing pseudo-boehmite with a phosphorus-containing compound and a sulfur-containing compound, and then molding, drying and optionally roasting to obtain a molded object;
(2) loading a hydrogenation active metal component on the formed object, and then optionally drying;
(3) activating the solid product obtained in the step (2), wherein the activating conditions comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours;
the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.
According to the present invention, the optional representation in step (1) means that this operation may or may not be performed. The present invention has a wide selection range of conditions for the calcination in step (1), and specifically, for example, the conditions may include: the temperature is 350-1000 ℃, preferably 400-800 ℃ and the time is 1-10 hours, preferably 2-6 hours.
According to the present invention, the calcination may not be performed in the step (1). It should be noted that, if the existing pseudo-boehmite is directly molded and dried without roasting, and then is loaded with the hydrogenation active metal component, the dispersibility of the hydrogenation active metal component is poor, but the inventor can meet the requirement of the dispersibility of the hydrogenation active metal component even if roasting is not performed because the pseudo-boehmite is mixed with the phosphorus-containing compound and the sulfur-containing compound. Under the condition, the formed product dried in the step (1) is directly loaded with the hydrogenation active metal component without roasting, and compared with the prior art, the method saves one-time roasting, has simpler operation steps, and is beneficial to reducing the energy consumption in the preparation process of the catalyst.
The present invention is not particularly limited to the drying in the step (1), and preferably, the drying conditions include: the drying temperature is 50-200 deg.C, and the drying time is 1-12 hr, preferably 80-150 deg.C, and the drying time is 2-8 hr. In the present invention, the drying method is not particularly limited, and for example, the drying may be at least one of drying, air-blast drying, spray drying, and flash drying. In the present invention, the drying atmosphere is not particularly limited, and may be performed in at least one of air, oxygen, and nitrogen, and air is preferable in order to reduce the production cost.
The present invention is not particularly limited to the mixing in step (1), and preferably, step (1) further includes: in the presence of a solvent (preferably water), pseudo-boehmite, a phosphorus-containing compound and a sulfur-containing compound are mixed, followed by molding.
The order of mixing in step (1) is not particularly limited in the present invention, and specifically, for example, a phosphorus-containing compound and a sulfur-containing compound may be directly mixed with pseudo-boehmite, followed by solvent mixing; or mixing the phosphorus-containing compound and the sulfur-containing compound with a solvent and then mixing with the pseudo-boehmite. The amount of the solvent used in the present invention is not particularly limited as long as it can provide an environment for mixing the pseudo-boehmite, the phosphorus-containing compound and the sulfur-containing compound, and the molding requirement can be satisfied, and those skilled in the art can select the amount according to the actual requirement according to the amount of the pseudo-boehmite, the phosphorus-containing compound and the sulfur-containing compound.
In the present invention, the requirement for molding is defined as that the weight ratio of the solvent to the powder (in the present invention, the solid material before molding) in the mixed material is appropriate, and the selection of the weight ratio is well known to those skilled in the art, for example, when molding by the bar-extruding technique, the weight ratio of the solvent to the powder is 0.4 to 2, preferably 0.5 to 1.5.
In the present invention, the molding is preferably extrusion molding. In order to ensure that the molding is carried out smoothly, an extrusion aid and/or a peptizing agent and optionally a pore-expanding agent can be added in the mixing process, wherein the types and the use amounts of the extrusion aid, the peptizing agent and the pore-expanding agent are known to those skilled in the art; for example, a common extrusion aid may be selected from at least one of sesbania powder, methyl cellulose, starch, polyvinyl alcohol and polyvinyl alcohol, the peptizing agent may be an inorganic acid and/or an organic acid, and the pore-expanding agent may be at least one of starch, synthetic cellulose, polymeric alcohol and a surfactant. Wherein, the synthetic cellulose is preferably at least one of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polymeric alcohol is preferably at least one of polyethylene glycol, polypropylene glycol and polyvinyl alcohol; the surfactant is preferably at least one of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, an allyl alcohol copolymer with molecular weight of 200-10000 and a maleic acid copolymer. The addition amounts of the extrusion aid, the peptizing agent and the optional pore-enlarging agent are not particularly limited in the invention, and can be selected conventionally in the field, and the invention is not described herein again.
The molded shape is not particularly limited in the present invention, and may be a shape conventionally used in the art, for example, the molded shape may be a clover shape, a butterfly shape, a cylindrical shape, a hollow cylindrical shape, a quadralobe shape, a pentalobal shape, a spherical shape, or the like.
The manner of loading the hydrogenation-active metal component on the molded article in step (3) is not particularly limited in the present invention, and may be any conventional method in the art, and may be, for example, a kneading method, a dry blending method, an impregnation method; preferably, the method for loading the hydrogenation active metal component on the formed object comprises the steps of impregnating the formed object with an impregnating solution containing at least one group VIB metal compound and at least one group VIII metal compound, and then drying.
According to the preparation method provided by the invention, further, the group VIB metal compound and the group VIII metal compound are respectively and independently selected from at least one of soluble compounds (including corresponding metal compounds soluble in water in the presence of a cosolvent). Specifically, the group VIB metal compound, for example, molybdenum, may be selected from salts and/or oxides of molybdenum-containing metals, for example, at least one selected from molybdenum oxide, molybdate, paramolybdate and phosphomolybdate, and preferably at least one selected from molybdenum oxide, ammonium molybdate, ammonium paramolybdate and phosphomolybdic acid; the group VIII metal compound may be selected from at least one of cobalt nitrate, cobalt acetate, cobalt hydroxycarbonate, and cobalt chloride, preferably cobalt nitrate and/or cobalt hydroxycarbonate, for example, cobalt, at least one of salts, oxides, and hydroxides containing nickel, for example, at least one of nitrates, chlorides, formates, acetates, phosphates, citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphides, sulfides, and oxides containing nickel, for example, at least one of oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, and oxides containing nickel, for example, and more preferably at least one of nickel nitrate, nickel acetate, nickel hydroxycarbonate, nickel chloride, and nickel carbonate.
According to the preparation method provided by the invention, the catalyst can also contain organic additives in the preparation process of the catalyst, such as the preparation process of soluble compounds of the VIB group metal compound and the VIII group metal compound. The method for introducing the organic additive is not particularly limited, and the organic additive may be introduced in any manner, for example, may be introduced together with the group VIII metal, may be introduced together with the group VIB metal element, may be introduced after introducing the group VIII and/or group VIB metal element, or may be introduced before introducing the group VIII and/or group VIB element. The invention is not particularly limited to the type of the organic additive, the organic additive is at least one selected from oxygen-containing and/or nitrogen-containing organic substances, the oxygen-containing organic substances are selected from organic alcohol and/or organic acid, and the nitrogen-containing organic substances are selected from at least one selected from organic amine and organic amine salt; specifically, the oxygen-containing organic matter is selected from at least one of ethylene glycol, glycerol, polyethylene glycol (molecular weight 200-; the nitrogen-containing organic substance is at least one selected from ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, EDTA and amine salts thereof, preferably EDTA and/or nitrilotriacetic acid.
Further, the present invention does not particularly limit the impregnation method and the impregnation time, and the impregnation method may be excess liquid impregnation, pore saturation impregnation, multiple impregnation, etc. depending on the amount of the impregnation liquid, and may be immersion method, spray impregnation, etc. depending on the manner of the impregnation; the impregnation time is preferably 0.5 to 3 hours. Further, by adjusting and controlling the concentration, amount or molding amount of the impregnation liquid, a specific content of the hydrogenation catalyst can be prepared, which is well known to those skilled in the art.
In the present invention, step (2) optionally means that the operation may be performed or may not be performed. Preferably, the hydrogenation-active metal component is supported on the molded article in the step (2), and then dried.
According to the production method provided by the present invention, the drying conditions in the method for supporting the hydrogenation active metal component on the shaped article are not particularly limited, and preferably, the drying conditions include: the drying temperature is 50-350 deg.C, and the drying time is 1-12 hr, preferably 80-250 deg.C, and the drying time is 2-8 hr. The present invention does not particularly limit the drying method, and the drying may be at least one of drying, air-blast drying, spray drying, and flash drying. The drying atmosphere in the present invention is not particularly limited, and may be at least one of air, oxygen and nitrogen, and is preferably air.
The inventor of the invention finds that the hydrogenation catalyst with a specific spinel structure can be formed by mixing the pseudo-boehmite, the phosphorus-containing compound and the sulfur-containing compound, then molding, drying and optionally roasting to obtain a molded product, then loading the hydrogenation active metal component on the molded product, and then activating at the temperature of 600-800 ℃ for 1-10 hours. If the activation temperature is too low or the activation time is too short, the content of spinel in the obtained catalyst is too low, and the hydrogenation activity and stability improvement effect of the hydrogenation active metal component is not obvious; if the activation temperature is too high or the activation time is too long, the spinel content in the obtained catalyst is too high, which affects the initial hydrogenation activity of the catalyst.
In a third aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:
mixing and molding pseudo-boehmite, a phosphorus-containing compound, a sulfur-containing compound and a precursor of a hydrogenation active metal component, and then sequentially drying and activating to obtain a hydrogenation catalyst; the conditions for the activation include: the temperature is 600 ℃ and 800 ℃, and the time is 1-10 hours;
the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.
The inventor of the invention finds that after pseudo-boehmite is mixed and formed with a precursor containing a phosphorus compound, a sulfur-containing compound and a hydrogenation active metal component, the hydrogenation catalyst can be obtained only by one-time drying and activation, the process of preparing a carrier by drying and roasting the pseudo-boehmite is omitted, the preparation process is simplified, and the hydrogenation catalyst with a specific spinel structure can be formed by activating at the temperature of 600-800 ℃ for 1-10 hours.
In the present invention, the manner of introducing the phosphorus-containing compound and the sulfur-containing compound is not particularly limited, and they may be introduced alone or in the form of a solution.
The order of mixing the pseudo-boehmite with the phosphorus-containing compound, the sulfur-containing compound, and the precursor of the hydrogenation active metal component is not particularly limited, and specifically, for example, the pseudo-boehmite may be mixed with the phosphorus-containing compound, then mixed with the sulfur-containing compound, and then mixed with the precursor of the hydrogenation active metal component; or mixing the pseudo-boehmite with a phosphorus-containing compound and a sulfur-containing compound, and then mixing with a precursor of the hydrogenation active metal component; or the boehmite, the phosphorus-containing compound and the sulfur-containing compound can be directly mixed with the precursor of the hydrogenation active metal component.
According to a preferred embodiment of the present invention, the method for mixing the pseudo-boehmite with the precursors containing the phosphorus-containing compound, the sulfur-containing compound and the hydrogenation-active metal component comprises uniformly mixing the phosphorus-containing compound, the sulfur-containing compound and at least one group VIB metal compound and at least one group VIII metal compound with the pseudo-boehmite, and then kneading the mixture.
In the present invention, the form of the precursor of the hydrogenation-active metal component is not particularly limited, and may be, for example, a solid powder of the hydrogenation-active metal component precursor or a solution of the hydrogenation-active metal component precursor.
In the present invention, there is no limitation on the precursor of the hydrogenation-active metal component, which is selected from at least one of a salt, an oxide, and a hydroxide of the hydrogenation-active metal component.
According to the present invention, preferably, the precursor of the group VIB metal component is selected from at least one of molybdenum oxide, molybdate, paramolybdate, phosphomolybdate, tungsten oxide and tungstate, more preferably from at least one of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, phosphomolybdic acid and ammonium metatungstate.
According to the present invention, preferably, the precursor of the group VIII metal component is selected from at least one of nitrate, chloride, formate, acetate, phosphate, citrate, oxalate, carbonate, hydroxycarbonate, hydroxide, phosphide, sulfide, aluminate and oxide of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel.
Specifically, the ranges of the group VIB metal compound and the group VIII metal compound according to the above second aspect may be selected accordingly, and the present invention is not described herein again.
According to a preferred embodiment of the present invention, the method of mixing the pseudo-boehmite with the precursors of the phosphorus-containing compound, the sulfur-containing compound and the hydrogenation-active metal component comprises kneading the pseudo-boehmite with a solution containing at least one group VIB metal compound and at least one group VIII metal compound, a solution of the phosphorus-containing compound and a solution of the sulfur-containing compound.
According to a preferred embodiment of the present invention, the preparation method of the hydrogenation catalyst comprises the steps of: the hydrogenation catalyst is prepared by kneading a solution containing at least one VIB group metal compound and at least one VIII group metal compound, a solution containing a phosphorus compound and a sulfur compound with pseudo-boehmite, molding, and then sequentially drying and activating.
According to the invention, organic additives may also be present during the preparation of the catalyst. The method for introducing the organic additive is not particularly limited, and the organic additive may be introduced in any manner, for example, may be introduced together with the group VIII metal, may be introduced together with the group VIB metal element, may be introduced after introducing the group VIII and/or group VIB metal element, or may be introduced before introducing the group VIII and/or group VIB element. The kind of the organic additive is not particularly limited in the present invention, and for example, the range of the kind of the organic additive according to the second aspect may be selected, and the present invention is not described herein again.
In the present invention, the molding method is not limited, and the molding can be performed according to a method conventional in the art, such as a roll ball method, a tablet method, and an extrusion molding method. The specific operation may be as described above in the second aspect, and is not described herein again.
The following relates to the production processes of the above-described second and third aspects, and the respective conditions may be the same or different, and each may be varied or preferably within the following ranges.
According to a preferred embodiment of the present invention, the temperature of the activation is 780-. In this preferred embodiment, it is more advantageous to increase the activity and stability of the hydrogenation catalyst.
In the present invention, the activation refers to activation that is conventional in the art, and the activation may be raised from an ambient temperature to an activation temperature, or may be raised from a drying temperature after the impregnation of the precursor directly to the activation temperature, and is not particularly limited. Preferably, the temperature rise rate of the activation is 50-600 deg.C/hr, preferably 100-550 deg.C/hr.
According to the invention, the phosphorus-containing compound is preferably used in such an amount that the resulting hydrogenation catalyst contains phosphorus in an amount of from 0.5 to 8% by weight, preferably from 1 to 6% by weight, calculated as oxide, based on the total amount of support.
The phosphorus-containing compound of the present invention may be an inorganic phosphorus-containing compound or an organic phosphorus-containing compound, and is preferably a water-soluble inorganic phosphorus-containing compound, and more preferably at least one phosphorus-containing compound selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, and potassium phosphate.
According to the invention, the sulfur-containing compound is preferably used in an amount such that the resulting hydrogenation catalyst contains 0.7 to 3% by weight, preferably 0.9 to 2.5% by weight, of elemental sulfur, based on the total amount of the support. In this preferred case, the activity and stability of the hydrogenation catalyst are better.
According to the present invention, preferably, the sulfur-containing compound comprises sulfuric acid and/or a metal sulfate.
The weight concentration of the sulfuric acid is not particularly limited in the present invention, and preferably, the weight concentration of the sulfuric acid is 1 to 10% by weight. The metal sulfate is selected from a wide range, and preferably, the metal sulfate is at least one selected from sodium sulfate, potassium sulfate, cobalt sulfate, nickel sulfate, ferric sulfate, tungsten sulfate and molybdenum sulfate, and preferably, the metal sulfate is sodium sulfate and/or potassium sulfate.
In the present invention, the ranges of the group VIB metal component and the group VIII metal component are as described above, and the present invention is not described herein again.
In the invention, the selection range of the amounts of the hydrogenation active metal component, the group VIB metal component and the group VIII metal component is wide, and preferably, the amount of the hydrogenation active metal component is such that the carrier content in the prepared hydrogenation catalyst is 30-99 wt% based on the total amount of the hydrogenation catalyst, the group VIB metal component content is 0.5-50 wt% and the group VIII metal component content is 0.5-20 wt% in terms of oxide.
Further preferably, the hydrogenation active metal component is used in an amount such that the obtained hydrogenation catalyst contains, based on the total amount of the hydrogenation catalyst, 40 to 94 wt% of a carrier, 5 to 45 wt% of the group VIB metal component and 1 to 15 wt% of the group VIII metal component, calculated as oxides. In this preferred case, the hydrogenation activity and stability of the hydrogenation catalyst are higher.
In a fourth aspect, the present invention provides a hydrogenation catalyst prepared by the preparation method as described above.
The hydrogenation catalyst prepared by the method has better activity and higher stability, and is particularly suitable for heavy oil hydrogenation reaction, so the fifth aspect of the invention provides the application of the hydrogenation catalyst in the heavy oil hydrogenation reaction. The hydrogenation catalyst provided by the invention can be used alone or combined with other catalysts when used for heavy oil hydrogenation reaction.
In the present invention, the hydrogenation catalyst may be presulfided according to a conventional method in the art before use to convert the active metal component supported thereon into a metal sulfide component; the prevulcanization method can be as follows: the hydrogenation catalyst is presulfided with sulfur, hydrogen sulfide or sulfur-containing raw materials in the presence of hydrogen at the temperature of 140 ℃ and 400 ℃. The prevulcanisation can be carried out either ex situ or in situ.
In the present invention, the hydrogenation conditions for the application of the hydrogenation catalyst are not particularly limited, and the reaction conditions generally used in the art may be employed; preferably, the reaction temperature is 200-420 ℃, and more preferably 220-400 ℃; the pressure is 2-18MPa, and the preferable pressure is 2-16 MPa; liquid hourly volume space velocity of 0.1-10h-1More preferably 0.15 to 6 hours-1(ii) a The hydrogen-oil volume ratio is 50 to 5000, and more preferably 50 to 4000.
The hydrotreating reaction apparatus in the application of the hydrogenation catalyst in the present invention is not particularly limited, and may be any reactor sufficient for the contact reaction of the feedstock oil with the hydrogenation catalyst under the hydrotreating reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor, or a fluidized bed reactor.
The present invention will be described in detail below by way of examples.
In the following examples, room temperature means 25 ℃ unless otherwise specified;
the reagents used in the following examples, except where specifically indicated, were all chemically pure reagents;
the dried gum powder was purchased from Changling catalyst Inc. under the designation RPB 90;
sesbania powder is produced by Shunhun commerce, Inc., Jiangsu Feng county;
in the following examples, the composition of the catalyst was determined by X-ray fluorescence spectroscopy (i.e., XRF) as described in petrochemical analysis method RIPP 133-90;
the formation of spinel structure of the metal component with aluminum in the catalyst was determined by ultraviolet visible spectroscopy (DRUVS). The instrument adopts a Cary300 ultraviolet visible light analyzer of Agilent company, and the wavelength ranges are as follows: 190nm-1100nm, wavelength precision: ± 0.1nm, wavelength reproducibility: ± 0.1nm, baseline stability: 0.0003/h, stray light: 0.02% or less, photometric accuracy: + -0.003.
Example 1
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
(1) taking 300 g of dry rubber powder, uniformly mixing the dry rubber powder with 5 g of sesbania powder to obtain a mixture, uniformly mixing the mixture with 11 g of ammonium dihydrogen phosphate and 0.36 l of 3% sulfuric acid aqueous solution by weight percentage at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into a trilobal wet strip with the outer diameter of 1.5 mm, drying the wet strip at 120 ℃ for 4h, and roasting the wet strip at 600 ℃ for 4h to obtain a formed product;
(2) taking 100g of the formed product in the step (1), and using 110 ml of the formed product containing MoO3160 g/L of NiO50 g/L of mixed solution of ammonium molybdate and nickel nitrate is soaked for 1 hour and dried for 4 hours at the temperature of 110 ℃;
(3) activating the solid product of the step (2), wherein the activating conditions comprise: the temperature is 700 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst C1 is obtained;
the composition and physicochemical properties of C1 are listed in table 1.
Comparative example 1
The preparation of the hydrogenation catalyst was carried out in the same manner as in example 1, except that the conditions for activation in step (3) included: the temperature is 500 ℃, the time is 42 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst D1 is obtained;
the composition and physicochemical properties of D1 are shown in table 1.
Comparative example 2
The preparation of a hydrogenation catalyst was carried out in the same manner as in example 1, except that ammonium dihydrogenphosphate was not added in the step (1), to obtain a hydrogenation catalyst D2;
the composition and physicochemical properties of D2 are shown in table 1.
Example 2
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
(1) taking 300 g of dry rubber powder, uniformly mixing the dry rubber powder with 5 g of sesbania powder to obtain a mixture, uniformly mixing the mixture with 15 g of ammonium dihydrogen phosphate and 0.36 l of 2% sulfuric acid aqueous solution by weight percentage at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into a butterfly-shaped wet strip with the outer diameter of 1.6 mm, drying the wet strip at 120 ℃ for 4h, and roasting the wet strip at 600 ℃ for 4h to obtain a formed product;
(2) 100g of the molded product obtained in step (1) was taken and immersed in 110 ml of an immersion liquid (containing MoO in terms of oxides)3160 g/L and NiO50 g/L ammonium molybdate and nickel nitrate) for 1 hour, and drying for 4 hours at 110 ℃;
(3) activating the solid product of the step (2), wherein the activating conditions comprise: the temperature is 700 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst C2 is obtained;
the composition and physicochemical properties of C2 are listed in table 1.
Example 3
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
(1) taking 300 g of dry rubber powder, uniformly mixing the dry rubber powder with 5 g of sesbania powder to obtain a mixture, uniformly mixing the mixture with 18 g of ammonium dihydrogen phosphate and 0.36 l of 5% sulfuric acid aqueous solution by weight percentage at room temperature, kneading the mixture into a plastic body on a double-screw extruder, extruding the plastic body into a four-leaf wet strip with the outer diameter of 1.2 mm, drying the wet strip at 120 ℃ for 4h, and roasting the wet strip at 600 ℃ for 4h to obtain a formed product;
(2) 100g of the molded product obtained in step (1) was taken and immersed in 110 ml of an immersion liquid (containing MoO in terms of oxides)3160 g/L and NiO50 g/L ammonium molybdate and nickel nitrate) for 1 hour, and drying for 4 hours at 110 ℃;
(3) activating the solid product of the step (2), wherein the activating conditions comprise: the temperature is 700 ℃, the time is 4 hours, the temperature rise rate of activation is 120 ℃/hour, and a hydrogenation catalyst C3 is obtained;
the composition and physicochemical properties of C3 are listed in table 1.
Example 4
The preparation of the hydrogenation catalyst according to the method of the invention comprises the following steps:
taking 300 g of dry rubber powder, uniformly mixing the dry rubber powder with 5 g of sesbania powder to obtain a mixture, and mixing the mixture with 11 g of ammonium dihydrogen phosphate and 0.12 liter of weight at room temperature9% strength by weight aqueous sulfuric acid solution, 0.22 l of a solution of a hydrogenation-active metal component (in terms of oxides, containing MoO)3160 g/l and NiO50 g/l of ammonium molybdate and nickel nitrate), then kneading the mixture into plastic bodies on a twin-screw extruder, extruding the plastic bodies into trilobal wet strips with the outer diameter of 1.5 mm, drying the wet strips at 120 ℃ for 3 hours, and then activating the wet strips, wherein the activation conditions comprise: the temperature is 700 ℃, the time is 4 hours, the temperature rise rate of activation is 100 ℃/hour, and a hydrogenation catalyst C4 is obtained;
the composition and physicochemical properties of C4 are listed in table 1.
Example 5
The preparation of the hydrogenation catalyst was carried out in the same manner as in example 1, except that the conditions for activation in step (3) included: the temperature is 730 ℃, the time is 3 hours, the temperature rise rate of activation is 100 ℃/hour, and a hydrogenation catalyst C5 is obtained;
the composition and physicochemical properties of C5 are listed in table 1.
Example 6
The preparation of the hydrogenation catalyst was carried out in the same manner as in example 1, except that the conditions for activation in step (3) included: the temperature is 650 ℃, the time is 6 hours, the temperature rise rate of activation is 100 ℃/hour, and a hydrogenation catalyst C6 is obtained;
the composition and physicochemical properties of C6 are listed in table 1.
Example 7
Preparation of a hydrogenation catalyst was carried out in the same manner as in example 1, except that in step (3)
The conditions for activation include: the temperature is 750 ℃, the time is 6 hours, the temperature rise rate of activation is 100 ℃/hour, and a hydrogenation catalyst C7 is obtained;
the composition and physicochemical properties of C7 are listed in table 1.
Example 8
Preparation of a hydrogenation catalyst was carried out in the same manner as in example 1, except that MoO was contained3160 g/L NiO50 g/L ammonium molybdate and nickel nitrate mixed solution is replaced by the mixed solution containing WO3220 g/L and NiO50 g/L of ammonium metatungstate and nickel nitrate mixed solution to obtainTo hydrogenation catalyst C8;
the composition and physicochemical properties of C8 are listed in table 1.
TABLE 1
| C1 | D1 | D2 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | |
| Q(F630/F500) | 1.6 | 1.1 | 1.6 | 1.8 | 1.7 | 1.8 | 2.0 | 1.5 | 2.1 | 1.7 |
| P2O5Per weight percent | 3.0 | 3.0 | - | 4.1 | 5.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| S/weight% | 1.6 | 1.6 | 1.6 | 1.1 | 2.9 | 1.6 | 1.6 | 1.6 | 1.6 | 1.6 |
| WO3Per weight percent | - | - | - | - | - | - | - | - | - | 18 |
| MoO3Per weight percent | 14.3 | 14.3 | 14.3 | 14.3 | 14.3 | 14.3 | 14.3 | 14.3 | 14.3 | - |
| NiO/weight% | 4.3 | 4.3 | 4.3 | 4.3 | 4.3 | 4.3 | 4.3 | 4.3 | 4.3 | 4.3 |
Note: s represents the content of sulfur in the carrier; p2O5Indicates the phosphorus content in the support as oxide.
Test example 1
This test example was used to test the hydrogenation activity and reaction stability of the hydrogenation catalysts in the examples.
The hydrogenation catalysts prepared in the above 100 ml examples 1 to 8, comparative example 1 and comparative example 2 were crushed into particles having a diameter of 2 to 3 mm, and then presulfidedThe conditions include: the vulcanized oil adopts 5 weight percent of dimethyl disulfide/Jingmen diesel oil, and the liquid hourly volume space velocity of the vulcanized oil is 1h-1The hydrogen partial pressure is 14MPa, the volume ratio of hydrogen to oil is 400, and the vulcanization is carried out for 3 hours at the constant temperature of 280 ℃; evaluation was then carried out in a 100 ml small fixed-bed reactor (catalyst loading 100 ml).
The specific properties of the heavy oil are shown in Table 2. At the reaction temperature of 380 ℃, the hydrogen partial pressure of 15MPa and the liquid hourly space velocity of 0.6h-1And carrying out a hydrogenation activity performance test under the condition that the volume ratio of hydrogen to oil is 600. Specifically, the Ni removal rate, V removal rate, desulfurization rate and carbon residue removal rate of the product after 600h reaction were tested, and the results are shown in Table 3;
the calculation methods of the Ni removal rate, the V removal rate, the desulfurization rate and the carbon residue removal rate are the same, and the calculation method is exemplarily illustrated by taking the Ni removal rate as an example:
the Ni removal rate is (Ni content in the raw material-Ni content in the hydrogenated product)/Ni content in the raw material;
the content of nickel (Ni) and vanadium (V) in the oil sample is measured by an inductively coupled plasma emission spectrometer (ICP-AES) (the used instrument is a PE-5300 type plasma photometer of PE company in America, and the specific method is shown in petrochemical engineering analysis method RIPP 124-90);
measuring the sulfur content in the oil sample by using an electric quantity method (the specific method is shown in petrochemical analysis method RIPP 62-90);
the content of carbon residue in the oil sample is determined by a micro-method (the specific method is shown in petrochemical analysis method RIPP 149-90).
TABLE 2
| Raw oil | Inferior heavy oil |
| Density (20 ℃), kg/m3 | 0.985 |
| Ni，μg/g | 26 |
| V，μg/g | 88 |
| S，％ | 4.2 |
| Residual carbon content% | 13.4 |
TABLE 3
| Example numbering | Ni removal rate/%) | Degree of V removal/%) | Desulfurization rate/%) | Percent carbon removal /) |
| Example 1 | 82 | 86 | 81 | 51 |
| Comparative example 1 | 77 | 79 | 74 | 46 |
| Comparative example 2 | 78 | 80 | 74 | 47 |
| Example 2 | 83 | 85 | 83 | 52 |
| Example 3 | 81 | 85 | 82 | 50 |
| Example 4 | 79 | 83 | 79 | 49 |
| Example 5 | 80 | 85 | 80 | 51 |
| Example 6 | 83 | 87 | 84 | 52 |
| Example 7 | 79 | 82 | 78 | 49 |
| Example 8 | 82 | 85 | 82 | 51 |
As can be seen from the data in Table 3, the hydrogenation catalyst prepared by the preparation method provided by the invention has better hydrogenation activity and higher stability, so that the operation period of the catalyst is prolonged, and the economic benefit of a refinery is improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
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| CN103055908A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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