CN117000277A - Residual oil hydrodemetallization catalyst and preparation method thereof - Google Patents
Residual oil hydrodemetallization catalyst and preparation method thereof Download PDFInfo
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- CN117000277A CN117000277A CN202210458865.7A CN202210458865A CN117000277A CN 117000277 A CN117000277 A CN 117000277A CN 202210458865 A CN202210458865 A CN 202210458865A CN 117000277 A CN117000277 A CN 117000277A
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- catalyst
- drying
- roasting
- solution
- mass
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 32
- 238000007598 dipping method Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 19
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000002028 Biomass Substances 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 9
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 238000004898 kneading Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 13
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 13
- 229920003169 water-soluble polymer Polymers 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000014633 carbohydrates Nutrition 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 150000002772 monosaccharides Chemical class 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 6
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
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- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
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- 238000010521 absorption reaction Methods 0.000 claims description 3
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- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 2
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- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 2
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
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- 239000002245 particle Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
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- 239000000843 powder Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 14
- 235000013162 Cocos nucifera Nutrition 0.000 description 11
- 244000060011 Cocos nucifera Species 0.000 description 11
- 238000011068 loading method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 229910002090 carbon oxide Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- -1 VIB metal compound Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J37/0215—Coating
-
- 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
- B01J37/08—Heat treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
The invention discloses a residual oil hydrodemetallization catalyst and a preparation method thereof. The method comprises the following steps: carrying out neutralization reaction on the acidic aluminum salt solution and the alkaline aluminum salt solution to obtain slurry; then carrying out primary aging, adding a water-soluble high polymer J1 after finishing, carrying out secondary aging, and drying to obtain a dried substance I; drying biomass raw materials, crushing the biomass raw materials into powder, mixing and kneading the powder with a polymer, a potassium-containing inorganic substance and a dried substance I in proportion, forming, and performing heat treatment to obtain a dried substance II; spraying the first impregnating solution on the dried material II in an unsaturated impregnating mode, drying and first roasting to obtain a roasted body, soaking the roasted body in a carbohydrate aqueous solution, and carbonizing after drying to obtain an intermediate; and spraying and dipping the second dipping liquid on the intermediate in a saturated dipping mode, and drying and second roasting to obtain the catalyst. When the catalyst is used for the hydrodemetallization reaction of residual oil, the activity and stability of the catalyst are both obviously improved.
Description
Technical Field
The invention relates to a hydrodemetallization catalyst, in particular to a hydrodemetallization catalyst applicable to a heavy oil, especially residual oil hydrotreatment process, and a preparation method and application thereof.
Background
It is well known that residuum hydrodemetallization is one of important chemical reactions occurring in residuum hydrotreatment, and various metal compounds react with H under the action of catalyst 2 The S reaction produces metal sulfides which are subsequently deposited on the catalyst and thus removed. The existence state of the active metal on the catalyst carrier can play an important role in the activity stability of the catalyst.
CN1289640a discloses a preparation method of supported hydrodemetallization catalyst, which adopts macroporous alumina carrier, and sprays ammonia solution or aqueous solution of active metal on the carrier in a spray-dipping roller pot, the method omits normal temperature drying process of the carrier after dipping, the sprayed carrier is directly placed in a roasting furnace with the temperature of 300-450 ℃ for roasting, then gradually rises to 460-550 ℃, and is kept at constant temperature for 1-5 h under air condition.
CN103785400a discloses a preparation method of a high-activity residual oil hydrodemetallization catalyst, which comprises the steps of impregnating an alumina carrier with a polyalcohol and/or monosaccharide aqueous solution, carrying out hydrothermal carbonization treatment in a sealed container after the impregnation is finished, then loading active metal components Mo and Ni on the carrier, and finally roasting the alumina loaded with the active components in a nitrogen atmosphere, and then roasting in an air atmosphere to obtain the residual oil hydrodemetallization catalyst. CN102441399a discloses a preparation method of hydrodemetallization catalyst, which prepares a group VIB metal compound and/or a group VIII metal compound into ammonia solution or aqueous solution, then impregnates an alumina carrier, and finally prepares the final catalyst through drying and roasting.
The activity and stability of the hydrodemetallization catalyst prepared by the method are still to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a residual oil hydrodemetallization catalyst and a preparation method thereof. The catalyst has higher activity and activity stability when being applied to the hydrodemetallization reaction of residual oil.
The first aspect of the invention provides a residuum hydrodemetallization catalyst comprising a carbon film coated intermediate and a second active component supported on the intermediate, the second active component comprising molybdenum and a group VIII metal; the intermediate comprises carbon, alumina, potassium oxide and a first active component comprising molybdenum and a group VIII metal; wherein the ratio of tetrahedral molybdenum to octahedral molybdenum content in the catalyst is 0.18-0.72 in terms of Mo atom, and the thickness of the carbon film is 0.1-400 μm, preferably 1-180 μm, and more preferably 25-70 μm.
In the invention, the carbon film is provided with macropores, and the pore volume of the carbon film layer is 0.9-2.0 cm 3 Preferably 1.0 to 1.8cm 3 Preferably 1.0 to 1.4cm per gram 3 And/g. The average pore diameter is 40 to 70nm, preferably 50 to 60nm.
In the present invention, the intermediate comprises carbon, alumina, potassium oxide and a first active component comprising molybdenum and a group VIII metal, wherein the group VIII metal is preferably nickel.
In the present invention, the group VIII metal in the second active component is preferably nickel.
In the invention, the catalyst also comprises an auxiliary component, wherein the auxiliary component is at least one selected from fluorine, phosphorus, silicon or boron, preferably phosphorus, and the content of the auxiliary component calculated by oxide is 1.0-4.0% based on the mass of the catalyst.
In the invention, the intermediate takes the mass of the intermediate as a reference, the carbon content is 5.0-7.0%, the alumina content is 76.0-82.0%, the potassium oxide content is 5.0-6.0%, and the balance is the first active metal.
In the invention, in the catalyst, moO is taken as a reference of the catalyst mass 3 The content of the metal oxide of the VIII family is 5.0 to 15.0 percent, and the content of the metal oxide of the VIII family is 1.0 to 5.0 percent.
In the invention, the total MoO in the catalyst 3 MoO in the first active component based on mass 3 The content of the second active component is 35.0% -65.0%, and MoO in the second active component 3 The content of (3) is 35.0-65.0%.
In the invention, the content of the VIII group metal oxide in the second active component is 35.0-65.0% based on the mass of the total VIII group metal oxide in the catalyst, and the content of the VIII group metal oxide in the second active component is 35.0-65.0%.
In the invention, the specific surface area of the catalyst is 180-230 m 2 The pore volume per gram is 0.7-1.2 mL/g, and the pore diameter can be 15-26 nm.
In the present invention, preferably, the specific surface area of the catalyst is 190 to 210m 2 The pore volume per gram is 0.8-1.0 mL/g, and the pore diameter can be 15-24 nm.
The second aspect of the invention provides a preparation method of the residuum hydrodemetallization catalyst, which comprises the following steps:
(1) Carrying out neutralization reaction on the acidic aluminum salt solution and the alkaline aluminum salt solution to obtain slurry;
(2) Aging the slurry obtained in the step (1) for the first time; after primary aging, adding a water-soluble high polymer J1, performing secondary aging, and drying to obtain a dried product I;
(3) Kneading and molding the biomass raw material, a high polymer, a potassium-containing inorganic substance and a dried substance I obtained in the step (2), and performing heat treatment to obtain a dried substance II;
(4) Spraying and dipping a first dipping liquid containing a first active component on the dried product II obtained in the step (3) in an unsaturated dipping mode, and drying and first roasting to obtain a roasted body;
(5) Soaking the roasting body obtained in the step (4) with a carbohydrate aqueous solution, drying and carbonizing to obtain an intermediate;
(6) Spraying and dipping a second dipping liquid containing a second active component on the intermediate obtained in the step (5) in a saturated dipping mode, drying and roasting for the second time, so as to obtain the catalyst.
In the step (1) of the invention, the acidic aluminum salt solution and the alkaline aluminum salt solution are added into a reaction kettle in a parallel flow mode.
In the step (1), the acidic aluminum salt solution is one or more of aluminum sulfate solution, aluminum nitrate solution or aluminum chloride solution; the acidic aluminum salt solution is prepared by using Al 2 O 3 The concentration is 5g/100 mL-25 g/100mL. The alkaline aluminum salt solution is one or two of sodium metaaluminate solution and potassium metaaluminate solution; the alkaline aluminum salt solution is prepared by using Al 2 O 3 The concentration is 8g/100 mL-52 g/100mL.
In the step (1), the temperature of the neutralization reaction is 75-120 ℃, the time is 30-150 minutes, and the pH value of the slurry is controlled to be 6.0-10.0 in the neutralization reaction process. The pH value of the slurry is regulated by controlling the adding rate of the acidic aluminum salt solution and the alkaline aluminum salt solution or adding an acid-base regulator additionally in the neutralization reaction process.
In the step (2), the primary aging temperature is 90-240 ℃, the time is 50-240 minutes, and the pH value is 8.5-12.0.
In the step (2), the water-soluble high polymer J1 is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like, and is preferably polyethylene glycol; the viscosity of the water-soluble polymer J1 (20 ℃) is 10 to 1000 mPas, and the viscosity of the slurry after the water-soluble polymer J1 is added (20 ℃) is 120 to 660 mPas.
In step (2) of the present invention, after the primary aging is completed, the slurry is preferably concentrated and then subjected to secondary aging. Wherein the volume of the concentrated slurry is 40-70% of the original volume.
In the step (2), the temperature of the secondary aging is 120-260 ℃ and the time is 45-190 minutes, and the temperature of the secondary aging is 30-60 ℃ higher than the temperature of the primary aging.
In the step (2), the drying temperature is 120-180 ℃ after secondary aging, the drying time is 2-10 h, and the filtering and washing can be carried out according to a conventional known method before drying. The dry matter content of the dried material I is 45-70wt%.
In the step (3), the biomass raw material is selected from one or more of wood, fruit shell, starch, bamboo or other biomass raw materials. The biomass raw material is dried and crushed into powder before use. The drying conditions are as follows: drying at 100-350 deg.c for 2-10 hr. The particle size of the powder is 100 to 450 mesh, preferably 200 to 400 mesh.
In the step (3), the high polymer is one or more of cellulose and resin, preferably one or more of hydroxypropyl cellulose, methyl cellulose and phenolic resin; the inorganic matter containing potassium is one or more of potassium carbonate, potassium hydroxide and potassium oxide.
In the step (3), the mass ratio of the total mass of the biomass raw material, the high polymer and the potassium-containing inorganic matters to the mass of the dried matters I is 1:5-15.
In the step (3) of the invention, conventional molding aids such as one or more of sesbania powder, cellulose and resin can be added according to the need in the molding process.
In the step (3) of the invention, the heat treatment conditions are as follows: treating at 100-400 deg.c for 0.5-3.0 hr at 20-120 deg.c/hr.
In the step (4), the dosage of the first impregnating solution accounts for 10-40% of the saturated water absorption of the dry matter II.
In step (4) of the present invention, the first impregnating solution is an impregnating solution containing Mo and a group VIII metal (preferably Ni), wherein the activityThe metal component molybdenum is one or two of molybdenum oxide and ammonium heptamolybdate, the nickel is one or two of basic nickel carbonate and nickel nitrate, and MoO is contained in the first impregnating solution 3 And the group VIII metal oxide content is 30.0 to 60.0g/100ml,5.0 to 30.0g/100ml, respectively. Wherein MoO introduced into the catalyst from the first impregnation liquid 3 In the amount of total MoO in the catalyst 3 35% -65% of load capacity; the amount of the group VIII metal oxide introduced into the catalyst from the first impregnation liquid is 35% to 65% of the total group VIII metal oxide loading in the catalyst.
In the step (4), at least one auxiliary agent containing fluorine, phosphorus, silicon or boron can be introduced into the first impregnating solution, and the addition amount of the auxiliary agent calculated by oxide is 18-28% of the total mass of the molybdenum oxide in the first impregnating solution, preferably 20-25%.
In the step (4) of the present invention, the first impregnating solution preferably further contains a water-soluble polymer J2. The water-soluble polymer J2 is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like. The viscosity of the water-soluble polymer J2 (20 ℃) is 10 to 1000 mPa.s, and the viscosity of the slurry after the water-soluble polymer J2 is added (20 ℃) is 150 to 800 mPa.s.
In the step (4), the dipping adopts a spray dipping method, and the spray dipping time is 15-35 min.
In the step (4), the drying temperature is 20-200 ℃ and the drying time is 2-12 h.
In the step (4) of the invention, the first roasting adopts temperature programming. The temperature rising rate is 1 ℃/min-3 ℃/min, the first roasting temperature is 500-750 ℃, the roasting time is 2-6 h, and the roasting atmosphere is inert atmosphere (such as nitrogen) or steam, preferably steam.
In the step (5), the carbohydrate solution is preferably an aqueous solution of starch and/or monosaccharide, wherein the mass percentage of the starch and/or monosaccharide in the solution is 10.0-40.0%; the monosaccharide comprises one or more of glucose, ribose, fructose, maltose, etc. And adding ammonium bicarbonate into the carbohydrate solution as a pore-expanding agent, wherein the mass percentage of the ammonium bicarbonate in the solution is 5.0-25.0%, and the soaking is performed for 30-240 seconds, preferably 40-120 seconds.
In the step (5) of the invention, the carbonization conditions are as follows: pre-oxidizing in air at 150-280 deg.c, preferably 170-260 deg.c, for 2-18 hr, preferably 2-12 hr; then carbonizing for 1-8 hours under nitrogen atmosphere at 400-650 ℃, preferably 450-600 ℃, and carbonizing the carbon film on the surface of the roasting body.
In the step (6) of the present invention, preferably, the second impregnation liquid contains an impregnation liquid of Mo and a group VIII metal (preferably Ni), wherein the active metal component molybdenum is one or both of molybdenum oxide and ammonium heptamolybdate, and the nickel is one or both of basic nickel carbonate and nickel nitrate. Wherein MoO introduced into the catalyst from the second impregnation liquid 3 In the amount of total MoO in the catalyst 3 35% -65% of load capacity; the amount of the group VIII metal oxide introduced into the catalyst from the second impregnation liquid is 35% to 65% of the total group VIII metal oxide loading in the catalyst.
In the step (6) of the invention, the second impregnating solution also contains a water-soluble high polymer J3. The water-soluble polymer J3 is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide, methylcellulose and the like. The viscosity of the water-soluble polymer J3 (20 ℃) is 10 to 1000 mPas, and the viscosity of the slurry after the water-soluble polymer J3 is added (20 ℃) is 150 to 800 mPas.
In the step (6), the dipping adopts a spray dipping method, and the spray dipping time is 15-35 min.
In the step (6), the drying temperature is 120-200 ℃ and the drying time is 2-12 h.
In the step (6) of the invention, the second roasting adopts temperature programming. The heating rate is 1 ℃/min-3 ℃/min, the second roasting temperature is 350-450 ℃, the roasting time is 2-6 h, and the roasting atmosphere is inert atmosphere (such as nitrogen) or steam, preferably steam.
Compared with the prior art, the invention has the following beneficial effects:
1. for hydrogenation catalysts, the reduction temperature of the tetrahedral Mo species is greater than that of the octahedral Mo species, and the presence of tetrahedral Mo adversely affects the weakening of the interaction between the support and the metal, thereby affecting catalyst activity and stability. The inventor finds out through a great deal of researches that firstly, the carrier is optimized, the slurry obtained after the neutralization reaction is aged for two sections, the water-soluble high polymer is added before the secondary aging, and the secondary aging is performed at a higher temperature, so that the porous material with proper specific surface area and good pore size distribution is obtained, namely the dried material I; drying biomass raw materials, crushing the biomass raw materials into powder, mixing and kneading the powder with a high polymer, an inorganic substance containing potassium and a dried substance I according to a proportion, forming, and performing heat treatment to obtain a dried substance II; spraying and dipping the first dipping liquid on the dried material II in an unsaturated dipping mode, drying and first roasting to obtain a catalyst roasting body; then soaking the obtained catalyst roasting body in a carbohydrate aqueous solution, drying, carbonizing, and forming a carbon film on the surface of the catalyst roasting body to obtain a catalyst intermediate; finally, the rest active metal is loaded on the intermediate in a saturated impregnation mode, and then the second roasting is carried out, so that the species proportion of tetrahedral molybdenum and octahedral molybdenum in the catalyst is proper, and preferably, water-soluble high polymers are added into the impregnating liquid for two times, so that the dispersion degree of the active metal can be promoted, and the acidity of the catalyst can be properly regulated. The carbon film formed on the surface of the roasting body not only adjusts the pore canal structure of the final catalyst, provides a proper reaction channel for diffusion of heavy oil or residual oil macromolecules, but also prevents catalyst coking deactivation caused by severe reaction of macromolecular compounds blocked in catalyst openings in residual oil at the early stage of reaction while improving the metal capacity of the catalyst, and on the other hand, the existence of the carbon film is mutually supplemented with the twice impregnation of active metal, so that the active metal is not only intensively distributed in the carbon film, but also widely distributed on the carbon film, the existence position and distribution mode of the active metal are effectively adjusted, and the utilization rate of the active metal is improved. The method of the invention improves the activity and stability of the residual oil hydrodemetallization catalyst obviously through the comprehensive coordination of the steps.
Drawings
FIG. 1 is a Raman spectrum of the catalyst surface obtained in example 1;
FIG. 2 is a Raman spectrum of the catalyst surface obtained in example 2;
FIG. 3 is a Raman spectrum of the catalyst surface obtained in comparative example 1;
FIG. 4 is a Raman spectrum of the catalyst surface obtained in comparative example 2.
Detailed Description
In the invention, a Thermo Scientific company DXR Microscope type DXR microscopic Raman spectrometer is adopted to carry out Raman spectrum characterization of the catalyst. Wherein at 930cm -1 The nearby peak is tetrahedral molybdenum peak, at 960cm -1 The nearby peaks are those of octahedral molybdenum, and the contents of tetrahedral molybdenum and octahedral molybdenum are calculated as the area at the same base line.
In the invention, the pore Structure (SVD) and specific surface area of the catalyst are characterized by using an ASAP-2420 physical adsorption instrument of Michael company.
The technical scheme and effect of the present invention will be further described with reference to the following examples, but is not limited to the following examples.
Example 1
1.5L of an aqueous solution of aluminum sulfate (as Al 2 O 3 The measured concentration is 10.0g/100mL, the initial temperature is 75 ℃, and 1L of sodium metaaluminate aqueous solution (Al is used) is introduced into a reaction kettle provided with 5L of water purification with a stirrer and a heating sleeve from the upper part 2 O 3 The concentration is 28.0g/100mL, the initial temperature is 110 ℃, the reaction kettle is filled with the solution from the bottom of the kettle, and the neutralization reaction temperature is controlled at 105 ℃; continuously adding an aluminum sulfate solution and a sodium metaaluminate solution, controlling the pH value to be 8.5, and reacting for 60 minutes; after the parallel flow is finished, carrying out primary aging, wherein the aging temperature is 140 ℃, the aging time is 120 minutes, and the aging pH value is 9.3; concentrating to slurry volume of 5L after primary aging, adding 100g of polyvinyl alcohol (viscosity of 30 mPas), adding polyvinyl alcohol, heating to 170 ℃ and carrying out secondary aging for 120 minutes, washing and drying at 120 ℃ for 6 hours to obtain a dry matter I with a dry basis of 50 wt%;
drying the coconut shell raw material at 120 ℃ for 6 hours, and then crushing the coconut shell raw material into 200-mesh coconut shell powder; coconut shell powder, hydroxypropyl cellulose, potassium hydroxide and a dried matter I are mixed according to the mass ratio of 0.5:0.5:0.5:8.5 weighing 1000g, kneading and forming; heating to 300 ℃ at a heating rate of 30 ℃/h, and then carrying out heat treatment on the molded product at 300 ℃ for 1h to obtain a dried product II;
with a first impregnating solution (MoO) 3 The content of NiO is 58.8g/100ml, the content of NiO is 11.5g/100ml, the addition amount of P (calculated as oxide) in the auxiliary phosphoric acid is 23.2% of the total mass of molybdenum oxide in the impregnating solution), the dried material II (the addition amount of the first impregnating solution is 20% of the saturated water absorption of the carrier) is sprayed, and polyacrylamide (the viscosity is 950 mPa.s) is added into the first impregnating solution, the viscosity after the addition is 600 mPa.s, wherein MoO is introduced into the catalyst by the first impregnating solution 3 In the amount of total MoO in the catalyst 3 40% of the loading; the amount of NiO introduced into the catalyst by the first impregnating solution is 40% of the total NiO loading in the catalyst, the spraying time is controlled within 30min, then the catalyst is kept stand and dried for 2h at the room temperature of 25 ℃, then the obtained sample is dried for 6h at 120 ℃ and roasted for 5h at 700 ℃, wherein the heating rate in the roasting process is 3 ℃/min, and a roasted body is obtained;
soaking the obtained roasting body in an aqueous solution with the mass percent of 6.0% of ammonium bicarbonate and the mass percent of 12.0% of starch for 40 seconds, taking out, pre-oxidizing in air for 3 hours at 180 ℃, carbonizing for 6 hours at 600 ℃ in nitrogen atmosphere, and forming a carbon film with the thickness of 28 mu m on the surface of the roasting body to obtain an intermediate; the alumina content was 77.2% and the sum of the carbon and potassium oxide content was 12.7%.
200g of intermediate is weighed, the second impregnating solution is subjected to secondary impregnation in a saturated impregnation mode, polyacrylamide (with the viscosity of 950 mPa.s) is added into the second impregnating solution, the viscosity of 400 mPa.s after the addition is carried out, and MoO introduced into the catalyst from the second impregnating solution 3 In the amount of total MoO in the catalyst 3 60% of the load; the amount of NiO introduced into the catalyst by the second impregnating solution is 60 percent of the total NiO loading in the catalyst, the spraying and impregnating time is controlled within 30 minutes, then the catalyst is dried for 6 hours at 120 ℃, and is roasted for 3 hours at 350 ℃, wherein the heating rate of the roasting process is 3 DEG CAnd/min to obtain the hydrodemetallization catalyst CAT-1. The physicochemical properties of the catalyst are shown in Table 1.
Example 2
The procedure is as in example 1, except that the initial temperature of the aqueous sodium metaaluminate solution to be added is 100℃and 110g of polyvinyl alcohol (viscosity: 30 mPas) is added after one aging, and the viscosity of the slurry (20 ℃) after the addition of polyvinyl alcohol is 280 mPas; soaking the obtained catalyst roasting body in an aqueous solution with the mass percent of 9.0% of ammonium bicarbonate and the mass percent of 18.0% of starch for 50 seconds, taking out, pre-oxidizing in air for 4 hours at 200 ℃, carbonizing for 5 hours at 550 ℃ in nitrogen atmosphere, and forming a carbon film with the thickness of 44 mu m on the surface of the roasting body to obtain an intermediate; wherein, the content of alumina is 77.0 percent, and the sum of the content of carbon and potassium oxide is 12.9 percent. In the first roasting process, the temperature is raised to 650 ℃ at a heating rate of 3 ℃/min for roasting for 4 hours; in the second roasting process, the temperature is raised to 400 ℃ at a heating rate of 3 ℃/min for roasting for 4 hours, and the hydrodemetallization catalyst CAT-2 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 3
The same as in example 1, except that the coconut shell raw material was dried at 120℃for 6 hours, and then pulverized into 200 mesh coconut shell powder; weighing 1000g of coconut shell powder, hydroxypropyl cellulose, potassium hydroxide and a dried product I according to the mass ratio of 0.4:0.4:0.4:8.8, kneading and forming; soaking the obtained catalyst roasting body in an aqueous solution with the mass percent of ammonium bicarbonate being 15% and the mass percent of glucose being 24% for 85 seconds, taking out, pre-oxidizing in air for 5 hours at 220 ℃, carbonizing for 4 hours at 500 ℃ in nitrogen atmosphere, and forming a 57-mu m thick carbon film on the surface of the roasting body to obtain an intermediate; wherein the alumina content is 77.8%, and the sum of the carbon and the potassium oxide content is 12.1%. In the first roasting process, the temperature is raised to 600 ℃ at a heating rate of 3 ℃/min for roasting for 3 hours; in the second roasting process, the temperature is raised to 450 ℃ at a heating rate of 3 ℃/min for roasting for 5 hours, and the hydrodemetallization catalyst CAT-3 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 4
The procedure of example 1 was followed except that the coconut shell raw material was dried at 120℃for 6 hours and then pulverized into 200 mesh coconut shell powder; coconut shell powder, hydroxypropyl cellulose, potassium hydroxide and a dried matter I are mixed according to the mass ratio of 0.3:0.3:0.3:9.1 weighing 1000g, kneading and forming; soaking the obtained catalyst roasting body in an aqueous solution with the mass percent of 24% of ammonium bicarbonate and the mass percent of 36% of glucose for 105 seconds, taking out, pre-oxidizing in air for 6 hours at 240 ℃, carbonizing for 3 hours at 450 ℃ in a nitrogen atmosphere, and forming a carbon film with the thickness of 66 mu m on the surface of the roasting body to obtain an intermediate; wherein, the content of alumina is 78.3 percent, and the sum of the content of carbon and potassium oxide is 11.6 percent. In the first roasting process, the temperature is raised to 550 ℃ at a heating rate of 3 ℃/min for 2 hours; in the second roasting process, the temperature is raised to 400 ℃ at a heating rate of 3 ℃/min for 6 hours, and the hydrodemetallization catalyst CAT-4 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 5
As in example 1, the difference is the MoO introduced into the catalyst from the first impregnation liquid 3 In the amount of total MoO in the catalyst 3 45% of the load; the amount of the VIII group metal oxide introduced into the catalyst by the first impregnating solution is 45 percent of the total VIII group metal oxide loading in the catalyst, and the spraying and impregnating time is controlled within 30 minutes; soaking the obtained catalyst roasting body in an aqueous solution with the mass percent of 9.0% of ammonium bicarbonate and the mass percent of 18.0% of starch for 120 seconds, taking out, pre-oxidizing in air for 5 hours at 220 ℃, carbonizing for 4 hours at 500 ℃ in nitrogen atmosphere, and forming a carbon film with the thickness of 49 mu m on the surface of the roasting body to obtain an intermediate; wherein the content of alumina is 77.5%, and the sum of the content of carbon and potassium oxide is 10.3%. In the second roasting process, the temperature rising rate of 3 ℃/min is increased to 400 ℃ for roasting for 3 hours, and the hydrodemetallization catalyst CAT-5 is prepared. The physicochemical properties of the catalyst are shown in Table 1.
Example 6
The procedure is as in example 1, except that, after the end of the parallel flow, the primary ageing is carried out at a temperature of 160℃for a period of 140 minutes and at a pH of 9.5; after the primary aging, the slurry was concentrated to a volume of 5L, 100g of polyvinyl alcohol (viscosity: 30 mPas) was added, the viscosity (20 ℃ C.) of the slurry after the addition of polyvinyl alcohol was 240 mPas, and the temperature was raised to 200 ℃ C., and the secondary aging was carried out for 140 minutes. Forming a carbon film with the thickness of 28 mu m on the surface of the roasting body to obtain an intermediate; the alumina content was 77.2% and the sum of the carbon and potassium oxide content was 12.7%. Finally preparing the hydrodemetallization catalyst CAT-6. The physicochemical properties of the catalyst are shown in Table 1.
Comparative example 1
Mixing the dried substance I (same as in example 1), 2.7wt% acetic acid and 2.5wt% sesbania powder, molding, drying at 150 ℃ for 5h, and roasting at 860 ℃ for 4h to prepare an alumina carrier; the carrier is directly immersed in saturated impregnating solution containing active metals Mo, ni and P, dried for 5 hours at 150 ℃, and then baked for 3 hours at 600 ℃ to prepare the hydrodemetallization catalyst dCAT-1. The physicochemical properties of this catalyst are shown in Table 1.
Comparative example 2
The hydrodemetallization catalyst dCAT-2 was obtained as in example 1, except that technical grade pseudo-boehmite was used directly for aging, and the calcined body was not subjected to any aqueous carbohydrate soaking treatment. The physicochemical properties of this catalyst are shown in Table 1.
Comparative example 3
The hydrodemetallization catalyst dCAT-3 was prepared as in example 1, except that the active metal solution was directly kneaded with coconut shell powder, hydroxypropyl cellulose, potassium hydroxide, and dried product I (in the same proportions as in example 1). The physicochemical properties of this catalyst are shown in Table 1.
TABLE 1 physicochemical Properties of hydrogenation catalysts
Evaluation test
The activity stability tests were carried out on the examples 1 to 6 and the comparative examples 1 to 3 on a 200ml fixed bed hydrogenation test apparatus, the properties of the raw oil are shown in Table 2, the test conditions are shown in Table 3, and the test results are shown in Table 4.
TABLE 2 oil Properties of raw materials
| Nature of raw oil | Middle eastern residuum |
| S，wt％ | 2.58 |
| Ni，μg/g | 34.7 |
| V，μg/g | 61.8 |
TABLE 3 test conditions
| Reaction temperature, DEG C | 390 |
| Reaction pressure, MPa | 16.0 |
| Liquid hourly space velocity, h -1 | 0.5 |
| Hydrogen to oil ratio, V/V | 800 |
Table 4 test results for hydrodemetallization catalysts of various examples
As can be seen from tables 1 and 4, the hydrodemetallization catalyst prepared by the method has higher specific surface area and pore volume, higher reaction activity and stability, and can well satisfy the hydrodemetallization process of heavy oil, especially residual oil.
Claims (19)
1. A residuum hydrodemetallization catalyst comprising a carbon film coated intermediate and a second active component supported on the intermediate, the second active component comprising molybdenum and a group VIII metal; the intermediate comprises carbon, alumina, potassium oxide and a first active component comprising molybdenum and a group VIII metal; wherein the ratio of tetrahedral molybdenum to octahedral molybdenum content in the catalyst is 0.18-0.72 in terms of Mo atom, and the thickness of the carbon film is 0.1-400 μm, preferably 1-180 μm, and more preferably 25-70 μm.
2. The catalyst according to claim 1, wherein the carbon film has macropores, and the pore volume of the carbon film layer is 0.9-2.0 cm 3 Preferably 1.0 to 1.8cm 3 Preferably 1.0 to 1.4cm per gram 3 /g; the average pore diameter is 40 to 70nm, preferably 50 to 60nm.
3. The catalyst of claim 1 wherein the group VIII metal in the first active component is nickel; preferably, the mass content of the carbon is 5.0-7.0%, the mass content of the alumina is 76.0-82.0%, the content of the potassium oxide is 5.0-6.0% and the balance is the first active component based on the mass of the intermediate.
4. The catalyst according to claim 1, wherein the total MoO in the catalyst is 3 MoO in the first active component based on mass 3 The content of the second active component is 35.0 to 65.0 percent based on the mass of the total VIII metal oxide in the catalystThe content of the VIII metal oxide is 35.0-65.0%.
5. The catalyst according to claim 1, wherein MoO is calculated on the basis of the catalyst mass 3 The content of the metal oxide of the VIII family is 5.0 to 15.0 percent, and the content of the metal oxide of the VIII family is 1.0 to 5.0 percent.
6. The catalyst according to claim 1, wherein the specific surface area of the catalyst is 180-230 m 2 Per gram, pore volume of 0.7-1.2 mL/g, pore diameter of 15-26 nm, preferably, specific surface area of 190-210 m 2 The pore volume per gram is 0.8-1.0 mL/g, and the pore diameter can be 15-24 nm.
7. Catalyst according to claim 1, characterized in that the catalyst further comprises an auxiliary component, which is at least one selected from fluorine, phosphorus, silicon or boron, preferably phosphorus, and the content of the auxiliary component is 1.0-4.0% in terms of oxide based on the mass of the catalyst.
8. The process for preparing the residuum hydrodemetallization catalyst of any of claims 1-7 comprising the steps of:
(1) Carrying out neutralization reaction on the acidic aluminum salt solution and the alkaline aluminum salt solution to obtain slurry;
(2) Aging the slurry obtained in the step (1) for the first time; after primary aging, adding a water-soluble high polymer J, performing secondary aging, and drying to obtain a dried substance I;
(3) Kneading and molding the biomass raw material, a high polymer, a potassium-containing inorganic substance and a dried material I obtained in the step (2), and performing heat treatment to obtain a dried material II;
(4) Spraying and dipping a first dipping liquid containing a first active component on the dried product II obtained in the step (3) in an unsaturated dipping mode, and drying and first roasting to obtain a roasted body;
(5) Soaking the roasting body obtained in the step (4) with a carbohydrate aqueous solution, drying and carbonizing to obtain an intermediate;
(6) Spraying and dipping a second dipping liquid containing a second active component on the intermediate obtained in the step (5) in a saturated dipping mode, drying and roasting for the second time, so as to obtain the catalyst.
9. The method of claim 8, wherein in step (1), the acidic aluminum salt solution and the basic aluminum salt solution are subjected to a cocurrent neutralization reaction; the acidic aluminum salt solution is prepared by using Al 2 O 3 The calculated concentration is 5g/100 mL-25 g/100mL; the alkaline aluminum salt solution is prepared by using Al 2 O 3 The calculated concentration is 8g/100 mL-52 g/100mL; preferably, in the step (1), the temperature of the neutralization reaction is 5-120 ℃, the time is 30-150 minutes, and the pH value of the slurry is controlled to be 6.0-10.0 in the neutralization reaction process.
10. The method according to claim 8, wherein in the step (2), the primary aging is carried out at a temperature of 90 to 240 ℃ for 50 to 240 minutes and at a pH of 8.5 to 12.0.
11. The preparation method according to claim 8, wherein in the step (2), the water-soluble polymer J1 is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methylcellulose, preferably polyethylene glycol; the viscosity of the water-soluble polymer J1 is 10 to 1000 mPas, and the viscosity of the slurry (20 ℃) after the water-soluble polymer J1 is added is 120 to 660 mPas.
12. The process according to claim 8 or 10, wherein in step (2), the secondary aging is carried out at a temperature of 120 to 260 ℃ for 45 to 190 minutes, the secondary aging is carried out at a temperature 30 to 60 ℃ higher than the primary aging, the drying temperature after the secondary aging is 120 to 180 ℃, the drying time is 2 to 10 hours, and the dry basis content of the dried product i obtained after the drying is 45 to 70wt%.
13. The method of claim 8, wherein in step (3), the biomass material is selected from one or more of wood, fruit shell, starch, bamboo or other biomass material, and the biomass material has a particle size of 100-450 mesh, preferably 200-400 mesh; and/or the polymer is one or more of cellulose and resin, preferably one or more of hydroxypropyl cellulose, methyl cellulose and phenolic resin; the potassium-containing inorganic matter is one or more of potassium carbonate, potassium hydroxide and potassium oxide; and/or, in the step (5), the carbohydrate solution is preferably an aqueous solution of starch and/or monosaccharide, wherein the mass percentage of the starch and/or monosaccharide in the solution is 10.0-40.0%; the monosaccharide comprises one or more of glucose, ribose, fructose and maltose.
14. The method according to claim 8, wherein in the step (3), the mass ratio of the total mass of the biomass raw material, the polymer and the potassium-containing inorganic substance to the dry substance i is 1:5 to 15; and/or, in the step (3), the heat treatment conditions are as follows: treating at 100-400 deg.c for 0.5-3.0 hr at 20-120 deg.c/hr.
15. The method according to claim 8, wherein in the step (4), the unsaturated impregnation is performed, and the first impregnation liquid is used in an amount of 10% to 40% of the saturated water absorption amount of the dry matter ii.
16. The method according to claim 8, wherein in step (4), the first impregnating solution is introduced with an additive containing at least one of fluorine, phosphorus, silicon or boron, the additive being added in an amount of 18 to 28% by weight, preferably 20 to 25% by weight, calculated as oxide, of the total mass of molybdenum oxide in the first impregnating solution.
17. The method according to claim 8, wherein in step (4), the drying temperature is 20 to 200 ℃, the drying time is 2 to 12 hours, the first baking temperature is 500 to 750 ℃, and the baking time is 2 to 6 hours, and the baking atmosphere is an inert atmosphere or steam, preferably steam; and/or in the step (6), the drying temperature is 120-200 ℃, the drying time is 2-12 h, the second roasting temperature is 350-450 ℃, the roasting time is 2-6 h, and the roasting atmosphere is inert atmosphere or steam, preferably steam.
18. The preparation method according to claim 8, wherein in the step (5), ammonium bicarbonate is added to the carbohydrate solution as a pore-enlarging agent, the mass percentage of the ammonium bicarbonate in the solution is 5.0% -25.0%, and the soaking is 30-240 seconds, preferably 40-120 seconds.
19. The method of claim 8, wherein in step (5), the carbonization conditions are: pre-oxidizing in air at 150-280 deg.c, preferably 170-260 deg.c, for 2-18 hr, preferably 2-12 hr; then carbonizing for 1-8 hours under nitrogen atmosphere at 400-650 deg.C, preferably 450-600 deg.C.
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