CN111957318A - Hydrotreating catalyst and preparation method and application thereof - Google Patents
Hydrotreating catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111957318A CN111957318A CN201910418463.2A CN201910418463A CN111957318A CN 111957318 A CN111957318 A CN 111957318A CN 201910418463 A CN201910418463 A CN 201910418463A CN 111957318 A CN111957318 A CN 111957318A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal oxide
- oxide matrix
- carrier
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 43
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000005416 organic matter Substances 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 13
- 235000000346 sugar Nutrition 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000010779 crude oil Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 229930182470 glycoside Natural products 0.000 claims description 3
- 150000002338 glycosides Chemical class 0.000 claims description 3
- 150000002402 hexoses Chemical class 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 150000002972 pentoses Chemical class 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 150000003641 trioses Chemical class 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000185 sucrose group Chemical group 0.000 claims description 2
- 150000005846 sugar alcohols Chemical class 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims 1
- 235000011044 succinic acid Nutrition 0.000 claims 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 37
- 239000003921 oil Substances 0.000 description 27
- 230000000694 effects Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000012072 active phase Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000004653 carbonic acids Chemical class 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 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 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000004005 microsphere Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000011164 primary particle Substances 0.000 description 1
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- 239000011163 secondary particle Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- -1 spheres Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
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Abstract
The invention discloses a hydrotreating catalyst, which comprises a metal active component and a carrier for loading the metal active component, wherein the metal active component comprises WO3NiO and MoO3The structure of the carrier comprises MgO and a metal oxide matrix containing the pore channels, wherein the MgO is uniformly dispersed in the metal oxide matrix containing the pore channels, and at least most part of the MgO is uniformly dispersed on the surface of the pore channels of the metal oxide matrix containing the pore channels. The hydrotreating catalyst has high desulfurizing, denitrifying and hydrogenating saturation performance, and is suitable for hydrotreating process of various kinds of distillate oil, especially for hydrorefining process with desulfurizing, hydrogenating denitrifying and hydrogenating saturation. The invention also discloses a preparation method and application of the hydrotreating catalyst.
Description
Technical Field
The invention relates to the technical field of catalysis. More particularly, it relates to a hydrotreating catalyst, its preparation method and application.
Background
With the aggravation of the heavy deterioration of crude oil in the world and the continuous upgrade of oil quality standards, in the face of the production of oil products with increasingly generalized national VI standards, oil refining enterprises need to further reduce the content of unsaturated hydrocarbons such as olefin, aromatic hydrocarbon, benzene and the like in the oil products while maintaining the processing and production of ultra-low sulfur gasoline and diesel oil (<10 ppm). For the oil refining industry, the improvement of the activity of the hydrogenation catalyst is undoubtedly the most economical way to ensure that multiple product indexes meet environmental protection indexes.
From the reaction mechanism of the hydrogenation process, the higher the degree of sulfidation of the catalyst is, the more the active phases are stacked in multiple layers, the more the Type II active phases are, the more the number of active centers at the corner positions of the active phases is, the more the hydrodesulfurization, hydrodenitrogenation and hydrosaturation reactions are facilitated. Typical commercial hydrogenation catalysts are in an oxidized state prior to being charged to a reactor and require sulfiding prior to use to achieve a sulfided state with true catalytic activity. Active metal Mo/W in the traditional oxidation state catalyst is easy to generate strong interaction (SMSI) with an alumina carrier, and can block the formation of a Type II active phase with a high number of layers, and if the SMSI can be effectively controlled, the improvement of the desulfurization, denitrification and hydrogenation saturation performance of the whole catalyst is facilitated.
CN101092573A is filled in a reactor and is contacted with a hydrogenation protective agent, a hydrofining catalyst I, a hydrofining catalyst II and an optional hydrofining catalyst III. The scheme fully exerts the advantages of respective catalysts in different desulfurization stages, and can obtain low-sulfur diesel oil meeting Europe III standard and Europe IV standard. Due to the demand for higher quality diesel, the activity of the catalyst needs to be further improved.
CN101591566A provides a catalyst grading scheme, dividing a reactor into four reaction zones, and sequentially filling a hydrogenation protective agent, a hydrofining catalyst I containing active metal Co-Mo, a mixture of the hydrofining catalyst I and the hydrofining catalyst II, and a hydrofining catalyst II containing active metal nickel-tungsten. The system improves the activity of the whole catalyst through the synergistic effect among all the catalysts. However, this system does not produce lower sulfur content diesel at lower reaction temperatures.
The filling mode is complex in the actual use process and is not beneficial to the regeneration of the catalyst. With the strictness of environmental standards and the decrease of the quality of diesel raw materials, a more ingenious catalyst preparation method is required to obtain a high-activity hydrogenation catalyst.
The CN108236965A patent discloses a modified hydrodesulfurization catalyst that employs a molecular sieve/alumina composite support impregnated with metallic Mg and mechanically mixed with citric acid. Mg (magnesium)2+Replaces tetrahedral Al in the alumina spinel structure3+The distribution of active components on the surface of the carrier is promoted, the vulcanization of Mo species is promoted, and the addition of Mg is beneficial to reducing SMSI (small surface area si) and enabling the catalyst to show higher reaction activity.
However, the present inventors have found in their research that Mg actually exerts a limited effect in the aforementioned conventional research methods, and thus has a limited effect on improving the catalytic performance of the catalyst.
Disclosure of Invention
An object of the present invention is to provide a hydrotreating catalyst which has high desulfurization, denitrification, and hydrogenation saturation properties at the same time, and is suitable for various distillate oil hydrotreating processes, particularly for hydrofining processes aimed at desulfurization, hydrodenitrification, and hydrogenation saturation.
The second object of the present invention is to provide a method for preparing a hydrotreating catalyst.
A third object of the present invention is to provide a use of a novel hydrotreating catalyst.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a hydrotreating catalyst comprising a metal active component and a carrier supporting the metal active component, wherein the metal active component contains WO3NiO and MoO3The structure of the carrier comprises MgO and a metal oxide matrix containing the pore channels, wherein the MgO is uniformly dispersed in the metal oxide matrix containing the pore channels, and at least most part of the MgO is uniformly dispersed on the surface of the pore channels of the metal oxide matrix containing the pore channels.
Optionally, the catalyst comprises, based on the total weight of the catalyst: WO3 5-40wt％，MoO3 5-30wt％，NiO0.1-15wt％，MgO0.1-5wt％。
Optionally, the catalyst comprises, based on the total weight of the catalyst: WO3 10-25wt％，MoO3 5-20wt％，NiO1-10wt％，MgO0.5-3wt％。
Optionally, the metal oxide matrix containing the pore channels is selected from one or more of alumina and alumina-silica; preferably, the alumina is γ -Al2O3。
Optionally, the hydrotreating catalyst further comprises an organic matter impregnated in the metal active component and/or the carrier.
Optionally, the organic matter is an oxygen-containing organic matter or a nitrogen-containing organic matter.
Optionally, the oxygen-containing organic matter is selected from one or more of organic alcohol and organic acid.
Optionally, the nitrogen-containing organic substance is an organic amine.
Alternatively, the molar ratio of organic to Ni in the hydrotreating catalyst is from 0.1 to 8, more preferably from 0.2 to 3.
In order to achieve the second purpose, the invention adopts the following technical scheme:
the preparation method of the hydrotreating catalyst comprises the following steps:
and uniformly mixing the carrier with a Ni-containing compound, a Mo-containing compound and a W-containing compound solution to obtain a mixture A, and drying or roasting to obtain the hydrotreating catalyst.
Optionally, the W-containing compound is selected from one or more of ammonium tungstate, ammonium metatungstate, ammonium paratungstate, and ammonium ethyl metatungstate.
Optionally, the Ni-containing compound is a water-soluble salt of Ni, preferably one or more of nitrate, acetate, carbonate, and basic carbonate of Ni.
Optionally, the Mo-containing compound is selected from one or more of molybdenum trioxide, ammonium paramolybdate and sodium molybdate.
Alternatively, the mixing is by co-impregnation or stepwise impregnation.
Optionally, the temperature for drying or roasting is 100-600 ℃, and the time is 3-24 hours.
Optionally, the preparation of the carrier comprises the following steps:
uniformly mixing the powder of the metal oxide matrix containing the pore channels with Mg solution and organic solvent, and then carrying out secondary drying and roasting on the obtained mixture in a non-oxidizing atmosphere to obtain a product B;
and mixing the product B with a binder, molding, drying and roasting to obtain the carrier.
Optionally, the Mg solution is selected from one or more of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate and magnesium chloride aqueous solution.
Optionally, the organic solvent is selected from one or more of water-soluble lower alcohols, lower carbonic acids, lower amines and sugars.
Optionally, the water-soluble lower alcohol is selected from ethylene glycol, glycerol, butanol, isopropanol, polyethylene glycol, diethylene glycol, butanediol, sugar alcohol.
Optionally, the lower acid is selected from citric acid, lactic acid, malic acid, tartaric acid, succinic acid, sugar acid.
Optionally, the lower amine is selected from sugar amines; the sugar is selected from sucrose, triose, pentose, hexose, and glycoside.
Optionally, the binder is an alumina precursor.
Optionally, the alumina precursor is selected from one or more of pseudo-boehmite, gibbsite, amorphous alumina and surge boehmite.
Optionally, the non-oxidizing atmosphere is an inert atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere.
Optionally, the roasting temperature in the non-oxidizing atmosphere is 150-350 ℃, and the roasting time is 2-8 hours.
Optionally, the mass ratio of the organic solvent to the porous metal oxide matrix is 10 to 50 wt%.
Optionally, the carbon content of the product B is 1-20 wt%, and the Mg content is 0.5-20 wt%.
Optionally, the mass ratio of the product B to the binder is 10 to 90 wt%.
Alternatively, the conditions for calcining the product B after forming and drying the mixture with the binder are as follows: the roasting temperature is 400 ℃ and 800 ℃, and the roasting time is 2-10 hours.
Optionally, the method for uniformly mixing the powder of the metal oxide matrix with the pore channels, the Mg solution and the organic solvent with the powder of the metal oxide matrix with the pore channels is to mix the Mg solution and the organic solvent with the powder of the metal oxide matrix with the pore channels at the same time, or mix the Mg solution with the powder of the metal oxide matrix with the pore channels first, and mix the obtained product with the organic solvent after drying.
Optionally, the preparation method further comprises the step of adding an organic substance to the mixture A.
In order to achieve the third purpose, the invention also provides the application of the hydrotreating catalyst in the hydrofining process of distillate oil or crude oil secondary processing products.
The invention has the following beneficial effects:
according to an object of the present invention, the hydrotreating catalyst provided in the present invention effectively adjusts the desulfurization, denitrification, and hydrogenation saturation properties of the catalyst by using an oxide of Ni-Mo-W as a metal active component in combination with at least most of MgO uniformly dispersed on the pore surfaces of a metal oxide matrix containing pores in a carrier. According to another object of the present invention, in the preparation method of the hydrotreating catalyst provided by the present invention, the organic solvent well protects Mg, and overcomes the defect that Mg cannot be sufficiently and uniformly distributed due to capillary condensation phenomenon, so that Mg is more and more uniformly dispersed and exposed on the surface of the pore channel of the matrix, thereby facilitating the interaction between Mg and the carrier and the active metal component, and facilitating the formation of a more reasonable pore structure, thereby facilitating the generation of a sulfidized active phase, and facilitating the improvement of the low temperature activity of the catalyst. In addition, the organic solvent also has a protective effect on the pore channels of the matrix, so that the pore channel structure can be protected in the preparation process of the carrier, the blockage of pores with smaller pore diameters is avoided, and the overall performance of the catalyst is finally improved. According to another object of the invention, the hydrotreating catalyst provided by the invention can be well used for catalyzing the hydrofining reaction of distillate oil or secondary processing products, and is particularly suitable for processes of hydrodesulfurization, hydrodenitrogenation and hydrogenation saturation of middle distillate oil.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In one aspect of the inventionOne embodiment provides a hydrotreating catalyst comprising a metal active component and a carrier supporting the metal active component, wherein the metal active component comprises WO3NiO and MoO3The structure of the carrier comprises MgO and a metal oxide matrix containing the pore channels, wherein the MgO is uniformly dispersed in the metal oxide matrix containing the pore channels, and at least most part of the MgO is uniformly dispersed on the surface of the pore channels of the metal oxide matrix containing the pore channels.
During research, the inventors of the present invention found that, in the current hydrotreating catalyst containing Mg, the reason why Mg cannot be sufficiently used for improving the catalytic activity of the hydrotreating catalyst is mainly that: at present, most of Mg element is generally added in the process of forming the carrier or is introduced by an impregnation mode after the carrier is formed. In the former, because Mg and pseudo-boehmite are fully mixed, pseudo-boehmite primary particles are converted into secondary particles through a roasting process, a part of Mg exists in an alumina framework and cannot be mostly exposed on the surface of a carrier pore channel, the pH value of the carrier is limited, the Mg acting with active metal is limited, and the utilization rate of Mg is reduced. In the latter, because of the processes of dipping and drying, in the drying process, along with the evaporation of the solvent, the Mg solution in the pore channels of the formed carrier is inevitably separated into a plurality of discontinuous small sections, so that the distribution of Mg element is not uniform, and the function of Mg element for adjusting the acidity of the carrier is reduced. In the hydrotreating catalyst of the invention, most MgO is uniformly dispersed on the pore channel surface of the metal oxide matrix containing the pore channel, so that the coking resistance of the obtained catalyst can be well improved, and in the catalyst structure, the MgO uniformly dispersed on the pore channel surface of the matrix is combined with metal active components containing W, Mo and Ni, so that the catalytic performance of the catalyst is effectively improved.
It is to be understood that, in the present embodiment, "at least most" includes both the concepts of "most" and "all". Wherein "the majority" is a content of more than 50 wt%.
In a preferred example, the catalyst comprises, based on the total weight of the catalyst: WO3 5-40wt％，MoO3 5-30wt％，NiO0.1-15wt％，MgO0.1-5wt％。
In yet another preferred example, the catalyst comprises, based on the total weight of the catalyst: WO3 10-25wt％，MoO3 5-20wt％，NiO1-10wt％，MgO0.5-3wt％。
In a preferred example, the metal oxide matrix containing the porous channels is selected from one or more of alumina and alumina-silica. Further, an exemplary porous containing metal oxide matrix is γ -Al2O3The catalyst effect of the hydrotreating catalyst obtained in this case is better.
In some examples, an organic substance may also be impregnated on the metal active component and/or the support. The complex impregnation technology is used for promoting the vulcanization of the active metal and promoting the synchronous vulcanization of the main agent and the auxiliary agent of the active metal, so that organic matters can be decomposed in the vulcanization process and the reaction process when the catalyst is used, the generation of a high-activity active phase is facilitated, and the activity of the catalyst is further enhanced. Exemplary organics are oxygen-containing organics or nitrogen-containing organics; the oxygen-containing organic matter is selected from one or more of organic alcohol and organic acid; the nitrogenous organic matter is organic amine. In the hydrotreating catalyst, the molar ratio of the organic substance to Ni is preferably 0.1 to 8, more preferably 0.2 to 3.
It will be appreciated that when the hydroprocessing catalyst is used, it may be presulfided by one skilled in the art in a conventional manner.
In still another aspect, according to still another embodiment of the present invention, there is provided a method for preparing a hydroprocessing catalyst, the method comprising the steps of:
and uniformly mixing the carrier with a Ni-containing compound, a Mo-containing compound and a W-containing compound solution to obtain a mixture A, and drying or roasting to obtain the hydrotreating catalyst.
In some preferred examples, the W-containing compound is selected from one or more of ammonium tungstate, ammonium metatungstate, ammonium paratungstate, and ammonium ethyl metatungstate; the Ni-containing compound is water-soluble salt of Ni, preferably one or more of nitrate, acetate, carbonate and alkali carbonate of Ni; the Mo-containing compound is one or more of molybdenum trioxide, ammonium paramolybdate and sodium molybdate.
In yet another preferred example, the manner of mixing is co-impregnation or stepwise impregnation. The impregnation sequence of each component is not required, and the impregnation can be realized.
In yet another preferred example, the drying or firing temperature is 100-. Further, the temperature of drying or baking may be further 100 ℃ to 500 ℃ for 3 to 18 hours.
In yet another preferred example, the preparation of the carrier comprises the steps of:
uniformly mixing the powder of the metal oxide matrix containing the pore channels with Mg solution and organic solvent, and then carrying out secondary drying and roasting on the obtained mixture in a non-oxidizing atmosphere to obtain a product B;
and mixing the product B with a binder, molding, drying and roasting to obtain the carrier.
The organic solvent is introduced in the preparation process of the carrier, the organic solvent and Mg are fully and uniformly mixed, and the organic solvent well protects Mg, so that more Mg is more and more uniformly dispersed on the surface of a pore channel of the substrate, the interaction between the Mg, the carrier and an active metal component is facilitated, the SMSI is effectively adjusted, the formation and dispersion of a high-activity Type II active phase are promoted, and the low-temperature catalytic performance of the catalyst is further improved.
In the preparation process of the carrier, the Mg solution and the organic solvent can be mixed with the powder of the metal oxide matrix containing the pore channel simultaneously or separately. When the two are mixed separately, the preferred mode is: uniformly mixing powder of the metal oxide matrix containing the pore channels with an Mg solution, and drying to obtain powder containing Mg; an organic solvent is then added to the Mg-containing powder. Wherein, the mixing mode of the powder of the metal oxide matrix containing the pore channels and the Mg solution is preferably dipping or beating; the manner of adding the organic solvent to the Mg-containing powder is preferably impregnation, more preferably equal-volume impregnation or supersaturation impregnation; the drying conditions are preferably: the drying temperature is 110-150 ℃, and the drying time is 3-12 hours. Further, when the Mg solution and the organic solvent are mixed with the powder of the metal oxide matrix having pores at the same time, the amounts of Mg and the organic solvent added are both larger than those in the case of separate mixing.
In a preferred example, the Mg solution includes, but is not limited to, one or more selected from an aqueous solution of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate, and magnesium chloride.
In a preferred example, the organic solvent includes, but is not limited to, one or more selected from the group consisting of water-soluble lower alcohols, lower carbonic acids, lower amines, and sugars.
In a preferred example, the water-soluble lower alcohol includes, but is not limited to, one or more selected from the group consisting of ethylene glycol, glycerol, butanol, isopropanol, polyethylene glycol (number average molecular weight of 500-; the lower acids include, but are not limited to, acids selected from citric acid, lactic acid, malic acid, tartaric acid, succinic acid, sugar acids; the lower amine is selected from sugar amine; the sugar includes, but is not limited to, sugars selected from sucrose, triose, pentose, hexose, glycosides.
In a preferred example, the binder is an alumina precursor. Exemplary alumina precursors include, but are not limited to, one or more selected from the group consisting of pseudoboehmite, boehmite, gibbsite, amorphous alumina, and surge.
In the above production method, the non-oxidizing atmosphere is preferably an inert atmosphere, and more preferably a nitrogen atmosphere or an argon atmosphere. In a preferred embodiment, the carbon content of the product B obtained after calcination in a non-oxidizing atmosphere is 1 to 20 wt%, preferably 2 to 10 wt%, and the Mg content is 0.5 to 20 wt%.
Further, the roasting temperature of roasting in the non-oxidizing atmosphere is 150-350 ℃, and the roasting time is 2-8 hours.
Further, the mass ratio of the product B to the binder is 10-90 wt%; the roasting conditions after the product B and the binder mixture are molded and dried are as follows: the roasting temperature is 400 ℃ and 800 ℃, and the roasting time is 2-10 hours.
In still another preferred example, the preparation method further includes a step of adding an organic substance to the mixture a. The organic matter is impregnated in the metal active component and/or the carrier. The organic substance is preferably an oxygen-containing organic substance or a nitrogen-containing organic substance. For example, the oxygen-containing organic matter is selected from one or more of organic alcohol and organic acid; the nitrogenous organic matter is organic amine; in the hydrotreating catalyst, the molar ratio of the organic matter to Ni is preferably 0.1 to 8, more preferably 0.2 to 3.
According to the method for preparing the catalyst provided by the embodiment, the carrier can be made into various easily-handled molded products, such as microspheres, spheres, tablets or strips, according to different purposes or requirements. The shaping can be carried out by conventional methods, such as extrusion, rounding, tabletting and the like. The extrusion molding method is preferably selected, and the shape of the catalyst is preferably selected from a strip clover or clover shape.
In a further aspect, an embodiment of the present invention provides the use of a hydrotreating catalyst as provided in the above embodiment in a hydrofinishing process of a distillate or crude oil secondary processed product.
The crude oil secondary processed product refers to a product of a crude oil deep processing process other than distillation, such as catalytic cracking oil, coking oil, thermal cracking oil, and the like. Wherein, the deep processing technology comprises but is not limited to: thermal cracking, catalytic cracking, delayed coking, catalytic reforming, hydrocracking, and the like.
The hydrotreating catalyst provided in the above embodiment can be used in a hydrorefining process of distillate oil or reforming pretreatment raw material, and is particularly suitable for a hydrotreating process of an oil product with high olefin content. The operation conditions can be adjusted within the following ranges according to the properties of the raw oil and the requirements on the quality of the oil products: the reaction temperature is 200 ℃ and 550 ℃, and the volume space velocity is 0.5-20h-1Hydrogen partial pressure of 0.5-15MPa, hydrogen/oil ratio of 50-900: 1.
the following description is given in conjunction with some specific examples:
analysis of the contents of the respective elements in the catalysts in the following examples and comparative examples were carried out by X-ray fluorescence spectrometer of ZSX Primus IV type, Japan, and carbon content on the powder was analyzed by Vario EL Cube Element analyzer, Element company, Germany.
Example 1
This example is a support for preparing a catalyst comprising the steps of:
(1) taking 200g of gamma-Al2O3The powder was thoroughly mixed with 2100mL of a 54g magnesium nitrate hexahydrate solution and dried at 120 ℃ for 3 hours to give Mg-containing gamma-Al2O3And (3) pulverizing. 200g of gamma-Al containing Mg2O3The powder was saturated and immersed in 192mL of an aqueous solution containing 30g of glycerin, dried at 120 ℃ and calcined at 215 ℃ for 3 hours in a nitrogen atmosphere (the content of C element in the powder was 5.3 wt%).
(2) 200g of the powder was mixed with 100g of pseudo-boehmite in a mass ratio of 2: 1. Then adding 9g of sesbania powder into the mixed powder, uniformly mixing, weighing 8.4mL of nitric acid and water to prepare 204mL of solution, adding the solution into the mixed powder under stirring, kneading, extruding to prepare a clover-shaped wet strip with the diameter of 1.6mm, subsequently drying the wet strip at 120 ℃ for 3h, and then roasting at 600 ℃ to obtain the Mg-containing gamma-Al2O3The carrier is marked as S1, and the three-dimensional projection electron microscope characterization shows that MgO is uniformly dispersed in gamma-Al in the carrier2O3And most of MgO is uniformly dispersed in the gamma-Al2O3The surface of the cell.
Example 2
This example is a support for preparing a catalyst comprising the steps of:
(1) taking 200g of gamma-Al2O3Mixing the powder with 460mL magnesium-containing solution containing 64.7g magnesium nitrate hexahydrate, pulping, and drying at 130 deg.C for 3 hr to obtain Mg-containing gamma-Al2O3And (3) pulverizing. 200g of the above Mg-containing gamma-Al2O3The powder was saturated and immersed in 134mL of an aqueous solution containing 30g of glycerin, dried at 120 ℃ and calcined at 215 ℃ for 2.5 hours in a nitrogen atmosphere (the carbon content in the powder was 5.3 wt%).
(2) 200g of the above powder was mixed with 66.7g of pseudo-boehmite in a mass ratio of 3: 1. Then adding 8g sesbania powder into the mixed powder, mixing uniformly, weighing 8.2mL nitric acid and water to prepare 187mL solution, adding the solution into the mixed powder under stirring, kneading, extruding to obtain clover-shaped wet strips with diameter of 1.6mm, and adding the wet strips into the mixtureDrying at 120 deg.C for 3h, and calcining at 600 deg.C to obtain Mg-containing gamma-Al2O3The vector has a structure similar to that of S1 and is marked as S2.
Example 3
This example is a support for preparing a catalyst comprising the steps of:
(1) taking 200g of gamma-Al2O3The powder was thoroughly mixed with 212mL of a solution containing 34.5g of magnesium nitrate hexahydrate and 29g of glucose, then dried at 120 ℃ for 3 hours and calcined at 260 ℃ under an argon atmosphere for 3 hours to obtain gamma-Al containing Mg and C2O3Powder (carbon content in powder 5.2 wt%).
(2) 200g of the above powder was mixed with 66.7g of pseudo-boehmite in a mass ratio of 3: 1. Then adding 8g of sesbania powder into the mixed powder, uniformly mixing, weighing 8.8mL of nitric acid and water to prepare 141mL of solution, adding the solution into the mixed powder under stirring, kneading, extruding to prepare a clover-shaped wet strip with the diameter of 1.6mm, subsequently drying the wet strip at 120 ℃ for 3h, and then roasting at 630 ℃ to obtain the Mg-containing gamma-Al2O3The vector has a structure similar to that of S1 and is marked as S3.
Example 4
This example is a process for preparing Ni-Mo-W/γ -Al2O3(S1) a catalyst comprising the steps of:
a82 mL solution was prepared from 26.44g of ammonium metatungstate, 13.9g of ammonium paramolybdate, 18.7g of nickel nitrate and a small amount of aqueous ammonia, 100g of S1 carrier was impregnated with the solution in the same volume, and after standing for 2 hours, the carrier was dried at 120 ℃ for 3 hours and calcined at 450 ℃ for 3 hours to obtain catalyst C1.
Example 5
This example is a process for preparing Ni-Mo-W/γ -Al2O3(S2) a catalyst comprising the steps of:
6g of MoO3Adding into 35mL of aqueous solution containing a small amount of phosphoric acid, heating to boil and dissolving, cooling to room temperature, adding 11.7g of ammonium metatungstate and 9.73g of nickel nitrate, slightly heating and stirring to dissolve, and fixing the volume to 40 mL. 50g of S2 carrier is soaked in the solution in equal volume, and after standing for 2h, the S2 carrier is dried at 120 ℃ for 3h and calcined at 450 ℃ for 3h to prepare the catalyst C2.
Example 6
This example is a process for preparing Ni-Mo-W/γ -Al2O3(S2) a catalyst comprising the steps of:
after 16.34g of ammonium paramolybdate was dissolved in 70mL of an aqueous solution containing a small amount of aqueous ammonia, 16.1g of ammonium metatungstate and 14.51g of nickel acetate were added and sufficiently dissolved by stirring, and a volume of 80mL was obtained. 100g of the S2 carrier was impregnated with the solution in equal volume, and after standing for 2 hours, the carrier was dried at 130 ℃ for 3 hours and calcined at 480 ℃ for 3 hours to obtain catalyst C3.
Example 7
This example is a process for preparing Ni-Mo-W/γ -Al2O3(S3) a catalyst comprising the steps of:
8g of MoO3Adding into 30mL of low-concentration phosphoric acid water solution, heating to boil, and cooling to normal temperature after dissolution. 18.79g of ammonium metatungstate and 27.5g of basic nickel carbonate were prepared into a 45mL aqueous solution under heating and stirring, and the two solutions were thoroughly mixed and impregnated with 100g of S3 carrier, and after standing for 2 hours, the mixture was dried at 130 ℃ for 3 hours and calcined at 480 ℃ for 3 hours, thereby obtaining catalyst C4.
Example 8
This example is to prepare a complex Ni-Mo-W/γ -Al2O3(S2) a catalyst comprising the steps of:
soaking 100g of S2 carrier in 80mL of aqueous solution containing 9g of ammonium metatungstate in equal volume, roasting at 420 ℃ for 3 hours, cooling to room temperature, preparing 74mL of solution from 12.7g of ammonium metatungstate, 13.25g of ammonium paramolybdate, 16.8g of nickel nitrate and 25.6 g of glycerol, soaking again in equal volume for 3 hours, drying at 120 ℃ for 3 hours, and drying at 160 ℃ for 4 hours to obtain the catalyst C5.
Comparative example 1
The comparative example is to prepare Ni-Mo-W/gamma-Al2O3(Mg and C-containing substances are not added in the preparation process) the catalyst comprises the following steps:
(1) 170g of gamma-Al are weighed2O3Mixing the powder with 50g of pseudo-boehmite powder, adding 6.5g of sesbania powder, uniformly mixing, measuring 6.2mL of concentrated nitric acid to prepare 182.5mL of nitric acid solution, and stirringAdding into the above mixed powder, kneading, extruding to obtain 1.6mm clover wet strip, oven drying at 140 deg.C for 3 hr, and roasting at 600 deg.C to obtain gamma-Al2O3And (3) a carrier.
(2) Preparing 84mL of solution from 16.2g of ammonium metatungstate, 16.5g of ammonium paramolybdate and 14.6g of nickel nitrate, and soaking 100g of gamma-Al obtained in the step (1) in the solution in equal volume2O3And drying the carrier at 130 ℃ for 3h, and roasting at 450 ℃ for 3h to obtain the catalyst D1.
Comparative example 2
The comparative example is to prepare Ni-Mo-W/Mg/gamma-Al2O3A catalyst comprising the steps of:
(1) weigh 180g of gamma-Al2O3Adding 6.2g of sesbania powder into 70g of pseudo-boehmite powder, uniformly mixing, measuring 8.3mL of concentrated nitric acid and 22.1g of magnesium nitrate to prepare 198mL of solution, adding the solution into the mixed powder under the stirring state, kneading and extruding to prepare clover-shaped wet strips containing Mg with the diameter of 1.6mm, subsequently drying the wet strips at 120 ℃ for 3h, and roasting at 600 ℃ to obtain the Mg-containing gamma-Al2O3And (3) a carrier.
(2) Preparing 84mL of solution from 16.2g of ammonium metatungstate, 16.5g of ammonium paramolybdate and 14.6g of nickel nitrate, and soaking 100g of gamma-Al obtained in the step (1) in the solution in equal volume2O3And drying the carrier at 130 ℃ for 3h, and roasting at 450 ℃ for 3h to obtain the catalyst D2.
The properties of the catalysts of examples 4 to 8 and comparative examples 1 to 2 are shown in Table 1 below.
TABLE 1 Properties of the catalysts
Test examples
The activity of catalysts C1-C5 was evaluated in this test example using straight-run diesel blended with 30% cat diesel and compared with the activity of the catalysts of comparative examples D1-D2. The properties of the feed oil are shown in Table 2.
TABLE 2 Properties of the feed oils
| Properties of crude oil | Numerical value |
| Density (20 ℃ C.), g/cm3 | 0.8867 |
| S，μg/g | 3246.8 |
| N，μg/g | 443.5 |
The activity evaluation of the catalyst was carried out in a 200mL fixed bed reactor, using a hydrogen one-pass procedure. Before the catalyst is evaluated, firstly, presulfurizing treatment is carried out, the vulcanized oil is hydrofined gasoline containing 2.5 percent, and the vulcanization conditions are as follows: the sulfuration pressure is 6.4MPa, the hydrogen/oil ratio is 500v/v, and the volume space velocity is 1.5h-1And after the air tightness of the device is qualified, carrying out constant-temperature vulcanization at 360 ℃ for 12 h. After the completion of the vulcanization, the vulcanized oil was switched to the raw oil, and after stabilization for 24 hours under the reaction conditions, the activity evaluation was started. The reaction conditions are as follows: the reaction pressure is 6.0MPa, and the Liquid Hourly Space Velocity (LHSV) is 2.5h-1The reaction temperature was 310 ℃ and the hydrogen/oil ratio was 300 v/v. The activity of each catalyst was analyzed after stable operation for 150 hours under the reaction conditions, and is specifically shown in table 3.
TABLE 3 evaluation test results of catalyst Activity
| Test example No. | Catalyst numbering | Sulfur content, μ g/g | Nitrogen content,. mu.g/g |
| Example 4 | C1 | 15.34 | 17.25 |
| Example 5 | C2 | 7.47 | 8.2 |
| Example 6 | C3 | 20.68 | 18.54 |
| Example 7 | C4 | 32.47 | 26.42 |
| Example 8 | C5 | 4.62 | 6.31 |
| Comparative example 1 | D1 | 112.83 | 98.57 |
| Comparative example 2 | D2 | 88.46 | 76.42 |
[ note)]The reaction conditions are as follows: the reaction pressure is 6.0MPa, and the Liquid Hourly Space Velocity (LHSV) is 2.5h-1The reaction temperature was 320 ℃ and the hydrogen/oil ratio was 300 v/v.
The results in table 3 show that the catalyst prepared by the method provided by the invention has significantly better S, N removal performance on the mixed diesel oil blended with 30% catalytic diesel oil than the conventional catalyst under the conditions of low pressure, lower reaction temperature and lower hydrogen-oil ratio, and the method of the invention is fully proved to be capable of effectively preparing the high-performance distillate oil hydrofining catalyst.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A hydrotreating catalyst characterized by comprising a metal active component and a carrier supporting the metal active component, wherein the metal active component contains WO3NiO and MoO3The structure of the carrier comprises MgO and a metal oxide matrix containing channels, and the MgO is uniformly dispersed in the metal oxide matrix containing the channels and at leastMost of the MgO is uniformly dispersed on the pore surfaces of the metal oxide matrix containing pores.
2. The hydrotreating catalyst according to claim 1, characterized in that the catalyst comprises, based on the total weight of the catalyst: WO3 5-40wt％，MoO35-30 wt%, NiO 0.1-15 wt%, MgO 0.1-5 wt%; preferably, the catalyst comprises, based on the total weight of the catalyst: WO3 10-25wt％，MoO3 5-20wt％，NiO 1-10wt％，MgO 0.5-3wt％。
3. The hydrotreating catalyst according to claim 1 or 2, characterized in that the metal oxide matrix containing channels is selected from one or more of alumina, alumina-silica; preferably, the alumina is γ -Al2O3。
4. The hydrotreating catalyst according to claim 1, characterized in that the hydrotreating catalyst further comprises an organic matter impregnated in the metal active component and/or the carrier; preferably, the organic matter is oxygen-containing organic matter or nitrogen-containing organic matter; preferably, the oxygen-containing organic matter is selected from one or more of organic alcohol and organic acid; the nitrogenous organic matter is organic amine; preferably, the molar ratio of organic to Ni in the hydrotreating catalyst is in the range of 0.1 to 8, more preferably 0.2 to 3.
5. The process for preparing a hydroprocessing catalyst according to any one of claims 1-4, comprising the steps of:
and uniformly mixing the carrier with a Ni-containing compound, a Mo-containing compound and a W-containing compound solution to obtain a mixture A, and drying or roasting to obtain the hydrotreating catalyst.
6. The preparation method according to claim 5, wherein the W-containing compound is selected from one or more of ammonium tungstate, ammonium metatungstate, ammonium paratungstate and ammonium ethyl metatungstate;
the Ni-containing compound is water-soluble salt of Ni, preferably one or more of nitrate, acetate, carbonate and alkali carbonate of Ni;
the Mo-containing compound is selected from one or more of molybdenum trioxide, ammonium paramolybdate and sodium molybdate;
preferably, the mixing is carried out by co-impregnation or stepwise impregnation;
preferably, the drying or baking temperature is 100-600 ℃ and the time is 3-24 hours.
7. The production method according to claim 5 or 6, wherein the production of the carrier comprises the steps of:
uniformly mixing the powder of the metal oxide matrix containing the pore channels with Mg solution and organic solvent, and then carrying out secondary drying and roasting on the obtained mixture in a non-oxidizing atmosphere to obtain a product B;
and mixing the product B with a binder, molding, drying and roasting to obtain the carrier.
8. The preparation method according to claim 7, wherein the Mg solution is one or more selected from magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate and magnesium chloride;
the organic solvent is selected from one or more of water-soluble low-carbon alcohol, low-carbon acid, low-carbon amine and sugar;
preferably, the water-soluble lower alcohol is selected from ethylene glycol, glycerol, butanol, isopropanol, polyethylene glycol, diethylene glycol, butanediol, sugar alcohol; the low-carbon acid is selected from citric acid, lactic acid, malic acid, tartaric acid, succinic acid and sugar acid; the lower amine is selected from sugar amine; the sugar is selected from sucrose, triose, pentose, hexose, glycoside;
preferably, the binder is an alumina precursor;
more preferably, the alumina precursor is selected from one or more of pseudo boehmite, gibbsite, amorphous alumina and surge boehmite;
preferably, the non-oxidizing atmosphere is an inert atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere;
preferably, the roasting temperature of roasting in the non-oxidizing atmosphere is 150-350 ℃, and the roasting time is 2-8 hours;
preferably, the mass ratio of the organic solvent to the metal oxide matrix containing the porous channel is 10 to 50 wt%;
preferably, the carbon content of the product B is 1-20 wt%, and the Mg content is 0.5-20 wt%;
preferably, the mass ratio of the product B to the binder is 10 to 90 wt%; the roasting conditions after the product B and the binder mixture are molded and dried are as follows: the roasting temperature is 400-;
preferably, the method for uniformly mixing the powder of the metal oxide matrix with the pore channel, the Mg solution and the organic solvent is to mix the Mg solution and the organic solvent with the powder of the metal oxide matrix with the pore channel at the same time, or mix the Mg solution with the powder of the metal oxide matrix with the pore channel, dry the obtained product and mix the dried product with the organic solvent.
9. The method according to claim 5, further comprising the step of adding an organic substance to the mixture A.
10. Use of a hydrotreating catalyst as claimed in any one of claims 1 to 4 in a hydrofinishing process of a distillate or crude oil secondary processing product.
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| CN113262795A (en) * | 2021-05-28 | 2021-08-17 | 中国海洋石油集团有限公司 | Catalyst for hydrodearsenicating and desulfurizing naphtha and preparation method thereof |
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|---|---|---|---|---|
| CN1169337A (en) * | 1996-06-28 | 1998-01-07 | 中国石油化工总公司 | Catalyst treated by distillate added with hydrogen and preparation method thereof |
| US20080146438A1 (en) * | 2006-12-19 | 2008-06-19 | Chuangsheng Bai | High activity supported distillate hydroprocessing catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169337A (en) * | 1996-06-28 | 1998-01-07 | 中国石油化工总公司 | Catalyst treated by distillate added with hydrogen and preparation method thereof |
| US20080146438A1 (en) * | 2006-12-19 | 2008-06-19 | Chuangsheng Bai | High activity supported distillate hydroprocessing catalysts |
Cited By (1)
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| CN113262795A (en) * | 2021-05-28 | 2021-08-17 | 中国海洋石油集团有限公司 | Catalyst for hydrodearsenicating and desulfurizing naphtha and preparation method thereof |
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