CN113231067A - Dearsenic agent for hydrogenation of light distillate oil and preparation method and application thereof - Google Patents
Dearsenic agent for hydrogenation of light distillate oil and preparation method and application thereof Download PDFInfo
- Publication number
- CN113231067A CN113231067A CN202110592907.1A CN202110592907A CN113231067A CN 113231067 A CN113231067 A CN 113231067A CN 202110592907 A CN202110592907 A CN 202110592907A CN 113231067 A CN113231067 A CN 113231067A
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- China
- Prior art keywords
- tio
- carrier
- roasting
- agent
- dearsenization
- 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.)
- Granted
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 97
- 239000002131 composite material Substances 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 150000002815 nickel Chemical class 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 11
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- 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 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 159000000003 magnesium salts Chemical class 0.000 claims description 8
- 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 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
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- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- 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 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 238000006477 desulfuration reaction Methods 0.000 abstract description 9
- 230000023556 desulfurization Effects 0.000 abstract description 9
- 239000011218 binary composite Substances 0.000 abstract description 6
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 229910052785 arsenic Inorganic materials 0.000 description 29
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 29
- 239000003921 oil Substances 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
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- 238000012360 testing method Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- -1 VIB group metals Chemical class 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 238000007580 dry-mixing Methods 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
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- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical group C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-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
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 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
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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Abstract
The invention relates to a dearsenic agent for hydrogenation of light distillate oil, a preparation method and application thereof, wherein the dearsenic agent comprises the following components in percentage by mass: NiO 5-20%, TiO210-35%, MgO 0.5-2.5%, C7-14%, and the rest is gamma Al2O3(ii) a Wherein the carrier in the dearsenization agent is TiO2‑γAl2O3The composite carrier comprises NiO as an active component and MgO and C as auxiliaries. Hydrodeoxygenation in the inventionArsenic as TiO2‑Al2O3Preparing binary composite carrier from TiO2By complexing to Al2O3In the pore canal structure, Al can be reserved2O3The integral framework can also exert TiO2The catalyst has excellent catalytic performance, improves the dispersion degree of active metal components, has higher catalytic activity and excellent stability, further ensures that the dearsenization agent has certain desulfurization performance through the design of the components, and improves the application range of the dearsenization agent.
Description
Technical Field
The invention relates to the field of catalytic dearsenization, in particular to a dearsenization agent for hydrogenation of light distillate oil and a preparation method thereof.
Background
In petroleum hydrocarbons, arsenic is most often present as an organic compound with the hydrocarbon radical. In the process of refining petroleum, arsenide respectively enters naphtha, gasoline and diesel oil, residual oil and other fractions according to the boiling point, and the arsenide is used as a harmful substance in hydrocarbon cracking, hydrogenation processes and catalytic reforming processes, thus seriously influencing the subsequent processing of crude oil.
The hydrogenation catalyst usually uses VIII group metal element as active component, and arsenic element in oil product existing in organic and inorganic forms is easily reduced into AsH under high temperature hydrogen condition3As (III) has strong reducibility and is easily bonded with d orbital electrons of a group VIII metal element to form a coordination bond to inactivate the toxicity, and the toxic form is difficult to eliminate by means of activation or regeneration. Even if the raw oil contains trace arsenic compound, the catalyst will be permanently poisoned and deactivated, which directly affects the operation stability of the device and shortens the operation period. Therefore, pre-dearsenification of feedstock is becoming increasingly important in order to ensure catalyst activity and long-term plant operation.
CN1055957C discloses a dearsenization agent for hydrocarbons, which is composed of 2-12 wt% of copper, 0-10 wt% of nickel and the balance of gamma-Al2O3Or amorphous aluminum silicate. However, before the dearsenization agent is used for dearsenization of hydrocarbons, reduction treatment is needed to be carried out by hydrogen so that at least part of Cu and Ni in the dearsenization agent is converted into a metal reduction state, the process is complex, and the energy consumption is increased.
US6759364B2 discloses a hydrocarbon hydrodearsenization agent, wherein a porous carrier is adopted to load metals, active metals are VIB group metals with the content of more than 8% and a certain amount of VIII group metals, and the atomic ratio of the VIII group metals to the VIB group metals is 1.5-2.5. Mainly comprises alumina, nickel with the content of more than 8 percent, molybdenum with the content of more than 8 percent and phosphorus with the content of 0.1 to 3 percent. The method is used for dearsenization of naphtha and light distillate, but the problems that diolefin polymerization is caused and coking is caused due to the fact that the content of olefin in naphtha is too high are not considered.
CN106660018A discloses a preparation method and a use method of a hydrocarbon hydrogenation dearsenization agent, wherein the catalyst comprises an alumina carrier, interlaminar molybdenum and phosphorus components and a nickel component covering layer. But the preparation process is complex and needs secondary impregnation.
CN105562000A discloses a normal temperature dearsenic agent and a preparation method and application thereof, the dearsenic agent comprises a carrier and a Cu-Ni active component loaded on the carrier, the Cu-Ni active component is CuO and NiO; the mass ratio of the carrier, the CuO and the NiO is 100 (1-10) to (1-10), and the carrier is used for removing inorganic arsenic in the catalytic cracking gasoline. Although the titanium-aluminum composite carrier is adopted in the dearsenization agent, the upper amount of active metal is low, secondary impregnation is needed, the dearsenization agent has low arsenic capacity, only inorganic arsenide in oil can be removed, and the raw material adaptability is poor.
CN108246302A discloses a preparation method of a catalytic gasoline hydrogenation dearsenic agent, and the dearsenic agent comprises 7-20 wt% of NiO and 2.5-4.9 wt% of MoO30-15 wt% of TiO2The balance being Al2O3Uniformly mixing alumina or a mixture of the alumina and the titanium oxide with sesbania powder, adding an organic polymer pore-forming agent, a binder and deionized water, kneading, extruding into strips, drying, and performing high-temperature heat treatment to obtain the dearsenic agent carrier. And carrying out hydrothermal treatment and pore expanding on the dearsenic agent carrier to obtain the dearsenic agent modified carrier. The dearsenization agent carrier is a mixture of alumina and titanium oxide, the simple dry mixing can not ensure the uniform mixing of the alumina and the titanium oxide, the specific surface of the carrier is small, the improvement of the activity of the dearsenization agent is not facilitated, and the size of the arsenic capacity is not reflected. In addition, the dearsenization agent is mainly suitable for dearsenization of catalytic gasoline, and has narrow raw material adaptability.
CN108246242A discloses a preparation method of a catalytic gasoline hydrogenation dearsenic agent, which comprises 7-20 wt% of NiO and 0-15 wt% of TiO2The balance being Al2O3Uniformly mixing alumina or a mixture of the alumina and the titanium oxide with sesbania powder, adding an organic polymer pore-forming agent, a binder and deionized water, kneading, extruding into strips, drying, and performing high-temperature heat treatment to obtain the dearsenic agent carrier. And carrying out hydrothermal treatment and pore expanding on the dearsenic agent carrier to obtain the dearsenic agent modified carrier. The dearsenic agent carrier is a mixture of alumina and titanium oxide, and simple dry mixing can not ensure the mixture of the alumina and the titanium oxideThe synthesis is uniform, the carrier ratio is smaller, the improvement of the activity of the dearsenization agent is not facilitated, and the size of the arsenic volume is not reflected. In addition, the dearsenization agent is mainly suitable for dearsenization of catalytic gasoline, and has narrow raw material adaptability.
However, the existing dearsenization agent still has the problems of poor raw material adaptability, such as secondary desulfurization treatment aiming at sulfur-containing components, high contents of olefin and oxygen in poor quality and catalytic gasoline naphtha, easy coking due to olefin polymerization in the processing process and the like.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a dearsenization agent for hydrogenation of light distillate oil and a preparation method thereof, wherein the dearsenization agent for hydrogenation has both desulfurization activity and strong anti-coking property, can effectively inhibit olefin polymerization, and is suitable for hydrodearsenization process of light distillate oil, including naphtha, catalytic gasoline, etc.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a dearsenic agent for hydrogenation of light distillate, which comprises the following components in percentage by mass: NiO 5-20%, TiO210-35%, MgO 0.5-2.5%, C7-14%, and the balance of gamma Al2O3；
Wherein the carrier in the dearsenization agent is TiO2-γAl2O3The composite carrier comprises NiO as an active component and MgO and C as auxiliaries.
The hydrodearsenicating agent in the invention is TiO2-Al2O3Preparing binary composite carrier from TiO2By complexing to Al2O3In the pore canal structure, Al can be reserved2O3The integral framework can also exert TiO2The catalyst has excellent catalytic performance, improves the dispersion degree of active metal components, has higher catalytic activity and excellent stability, further ensures that the dearsenization agent has certain desulfurization performance through the design of the components, and improves the application range of the dearsenization agent.
In the present invention, NiO in the dearsenizing agent may be 5 to 20% by mass, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20% by mass, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the invention, TiO in the dearsenic agent2The content of 15 to 35% by mass may be, for example, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% or the like, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the present invention, the amount of MgO in the dearsenization agent is 0.5 to 2.5% by mass, and may be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, or 2.5%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the content of C in the dearsenization agent is 7 to 14% by mass, and may be, for example, 7%, 8%, 9%, 10%, 11%, 12%, 13%, or 14%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As a preferable technical scheme of the invention, the dearsenic agent comprises the following components in percentage by mass: NiO 8-16%, TiO215-35%, MgO 1-1.5%, C8-12%, and the balance of gamma Al2O3。
In a second aspect, the present invention provides a method for preparing the dearsenic agent according to the first aspect, the method comprising the steps of:
(1) adding TiO into the mixture2-γAl2O3Mixing the composite carrier with the pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier;
(2) and (2) carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and then sequentially carrying out second drying and second roasting to obtain the dearsenic agent.
As a preferable technical solution of the present invention, the TiO described in the step (1)2-γAl2O3The composite carrier is prepared by a precipitation method, a coprecipitation method or a sol-gel method.
Wherein, gamma Al in the precipitation method2O3Prepared by roasting pseudo-boehmite powder for 3-5h in the air atmosphere of 550-600 ℃. The aluminum source for the coprecipitation method or the sol-gel method may be an aluminum source such as aluminum salt and the like which are conventional in the art.
In the present invention, the temperature during the calcination is 550-600 ℃, for example 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃ or 600 ℃, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the time for baking in the air atmosphere is 3 to 5 hours, and may be, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the specific surface area of the pseudo-boehmite powder is 220-270m2Per g, pore volume of 0.7-1.2cm3(ii)/g, the average pore diameter is 5 to 25nm, and pores having a pore diameter of 4 to 10nm account for more than 20% of the total pores.
In the invention, the specific surface area of the pseudo-boehmite powder is 220-270m2Per g, for example, may be 220m2/g、230m2/g、240m2/g、250m2/g、260m2G or 270m2And/g, but are not limited to the values recited, and other values not recited within the range are equally applicable.
In the invention, the pore volume of the pseudo-boehmite powder is 0.7-1.2cm3Per g, may be, for example, 0.7cm3/g、0.75cm3/g、0.8cm3/g、0.85cm3/g、0.9cm3/g、0.95cm3/g、1cm3/g、1.05cm3/g、1.1cm3/g、1.15cm3G or 1.2cm3And/g, but are not limited to the values recited, and other values not recited within the range are equally applicable.
In the present invention, the mean pore diameter of the pseudo-boehmite powder is 5 to 25nm, and may be, for example, 5nm, 15nm, 20nm or 25nm, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the titanium source in the preparation process of the composite carrier in step (1) comprises 1 or a combination of at least 2 of titanium sulfate, titanium nitrate, titanium acetate or titanium trichloride, and is preferably titanium sulfate.
Preferably, the titanium source and the gamma Al are generated during the preparation process of the composite carrier in the step (1)2O3The mass ratio is (0.74 to 1.73):1, and may be, for example, 0.74:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1 or 1.7:1, but is not limited to the values listed, and other values not listed in the range are also applicable.
In a preferred embodiment of the present invention, the pretreatment liquid in step (1) is an aqueous solution of a water-soluble organic substance and a magnesium salt.
Preferably, the water-soluble organic substance comprises 1 or a combination of at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid, acetic acid, preferably glucose and/or sucrose.
Preferably, the amount of the water-soluble organic substance added to the pretreatment liquid in the step (1) is the amount of the TiO calculated by carbon element2-γAl2O3The amount of the composite carrier is, for example, 9.6 to 17% by mass, and may be, for example, 9.6%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, or 17%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the magnesium salt comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium sulfate, magnesium acetate, basic magnesium carbonate, or magnesium chloride.
Preferably, in the pretreatment liquid in the step (1), the amount of the magnesium salt added is in terms of magnesium oxide to the TiO2-γAl2O3The amount of the composite carrier is, for example, 1.2 to 2.1% by mass, and may be, for example, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 2% or 2.1% by mass, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Are preferred techniques of the present inventionThe procedure of (1) mixing the TiO2-γAl2O3The solid-to-liquid ratio g/mL of the composite carrier to the pretreatment liquid is 1 (0.8 to 0.9), and may be, for example, 1:0.8, 1:0.81, 1:0.82, 1:0.83, 1:0.84, 1:0.85, 1:0.86, 1:0.87, 1:0.88, 1:0.89 or 1:0.9, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As a preferred embodiment of the present invention, the temperature of the first drying in step (1) is 100-150 ℃, and may be, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the first drying time in step (1) is 3-6h, such as 3h, 4h, 5h or 6h, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the first firing of step (1) is performed under a protective atmosphere comprising nitrogen or an inert gas.
Preferably, the temperature of the first calcination in step (1) is 500-.
Preferably, the first calcination time in step (1) is 4-8h, such as 4h, 5h, 6h, 7h or 8h, but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferred technical solution of the present invention, the nickel salt in the nickel salt solution in step (2) includes 1 or a combination of at least 2 of nickel nitrate, basic nickel carbonate, nickel acetate and nickel citrate, and is preferably nickel nitrate.
Preferably, the nickel content in the nickel salt solution in the step (2) is 9.5-10.23% by mass, for example, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 10.1%, 10.2% or 10.23% by mass, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the solid-to-liquid ratio of the carrier and the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15):1, and may be, for example, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.1:1 or 1.15:1, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the temperature of the second drying in step (2) is 110-140 ℃, such as 110 ℃, 120 ℃, 130 ℃ or 140 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the second drying time in step (2) is 2-5h, such as 2h, 3h, 4h or 5h, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the temperature of the second calcination in step (2) is 400-.
Preferably, the second calcination time in step (2) is 3-6h, such as 3h, 4h, 5h or 6h, but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) adding TiO into the mixture2-γAl2O3Mixing the composite carrier with the pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier;
(2) carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and then sequentially carrying out second drying and second roasting to obtain the dearsenic agent;
the pretreatment liquid in the step (1) is a water solution of water-soluble organic matters and magnesium salts; the water-soluble organic substance comprises 1 or at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid and acetic acid2-γAl2O3The solid-liquid ratio g/mL of the composite carrier to the pretreatment liquid is 1 (0.8-0.9); the first roasting is carried out in a protective gasThe method is carried out under the atmosphere, and the protective atmosphere comprises nitrogen or inert gas; the temperature of the first roasting is 500-800 ℃; the first roasting time is 4-8 h;
the solid-to-liquid ratio of the carrier to the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15): 1; the second roasting is carried out under a protective atmosphere, wherein the protective atmosphere comprises nitrogen or inert gas; the temperature of the second roasting is 400-600 ℃; the time of the second roasting is 3-6 h.
In a third aspect, the invention provides the use of the dearsenization agent according to the first aspect for dearsenization in hydrogenation of light distillate, wherein the dearsenization agent is sulfurized before use. The sulfuration condition is 220-300 ℃, sulfuration is 7-30h, the hydrogen partial pressure is 1-2MPa, the hydrogen-oil volume ratio (100-300):1, the distillate oil hydrogenation dearsenification reaction condition is as follows: the reaction pressure is 1-4MPa, the reaction temperature is 240--1-50h-1。
The temperature is 220 ℃ to 300 ℃, and may be, for example, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
The vulcanization time is 7 to 12 hours, for example, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc., and the hydrogen partial pressure is 1 to 2MPa, for example, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa or 2MPa, etc., but not limited to the values mentioned above, and other values not mentioned in the above range are also applicable.
The hydrogen-oil volume ratio (100-.
The reaction conditions of distillate oil hydrogenation dearsenification are as follows: the reaction pressure is 1 to 4MPa, and may be, for example, 1MPa, 2MPa, 3MPa or 4MPa, but is not limited to the values listed, and other values not listed in the range are also applicable.
The reaction temperature is 240 ℃ to 320 ℃, and may be, for example, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃ or 320 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
The hydrogen-oil volume ratio (100- & ltSUB- & gt 300) & gt, 1, can be, for example, 100:1, 150:1, 200:1, 250:1, or 300:1, but is not limited to the values listed, and other values not listed in this range are also applicable.
The volume space velocity is 10-50h-1For example, it may be 10h-1、20h-1、30h-1、40h-1Or 50h-1And the like, but are not limited to the recited values, and other values not recited within the range are equally applicable.
In the invention, the addition amount which is not explained in the preparation process can be obtained by deducing the content of each component in the product.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the hydrodearsenicating agent in the invention is TiO2-Al2O3Preparing binary composite carrier from TiO2To Al2O3In the pore canal structure, Al can be reserved2O3The integral framework can also exert TiO2The catalyst has excellent catalytic performance, improves the dispersion degree of active metal components, and shows higher catalytic activity and excellent stability.
(2) The hydrogenation dearsenization agent carrier of the invention introduces magnesium and carbon by resetting the components, increases the specific surface pore volume, adjusts the catalytic hydrogenation saturation performance of the catalyst, effectively avoids coking caused by olefin polymerization in light distillate oil, and can be used for removing arsenic in catalytic cracking gasoline rich in unsaturated hydrocarbon.
Drawings
FIG. 1 is a graph showing the acidity of catalysts obtained in example 1 of the present invention and comparative example 1.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a dearsenic agent for hydrogenation of light distillate, which comprises the following components in percentage by mass: NiO 14%, TiO215 percent of MgO 1 percent, 10 percent of C and the balance of gamma Al2O3；
Wherein the carrier in the dearsenization agent is TiO2-γAl2O3The composite carrier comprises NiO as an active component and MgO and C as auxiliaries.
The preparation method comprises the following steps:
1) weighing 90.2g of titanium sulfate, placing the titanium sulfate in 500mL of deionized water, stirring and dissolving, and taking 120g of gamma-Al obtained by roasting pseudo-boehmite powder at 580 DEG C2O3Adding the mixture into a titanium sulfate solution, slowly dropwise adding ammonia water under the stirring state, adjusting the pH value to 8, precipitating and aging for 3 hours, filtering by vacuum filtration, repeatedly washing by deionized water, placing the obtained white solid in a 120 ℃ oven for drying for 3 hours, placing in a tubular furnace for roasting at 580 ℃ to obtain TiO2-Al2O3Composite carrier, denoted as mixed powder FT 1.
(2) 120mL of deionized water was measured by a measuring cylinder and added to the beaker, and 50.0g of glucose and 12.7g of Mg (NO) were further measured3)2Adding the mixture, stirring for 20min, dissolving completely, mixing uniformly, and metering to 140 mL. Adding the solution into mixed powder FT1 for 3 times, kneading, extruding into 1.6 mm-diameter clover-shaped wet strips, drying at 120 deg.C for 5 hr, and roasting at 650 deg.C under nitrogen atmosphere for 4 hr to obtain TiO containing Mg and carbon2-Al2O3The binary composite carrier, namely the hydrogenation dearsenization agent carrier, is recorded as ZT 1.
(3) 109.0g of nickel nitrate hexahydrate is weighed and added into 70mL of deionized water, the mixture is stirred until metal salts are completely dissolved, the volume is fixed to 130mL, 172g of carrier ZT1 is soaked in the solution in the same volume, then the carrier ZT1 is dried for 3h at 120 ℃, and the carrier ZT1 is roasted for 3h at 450 ℃ in a nitrogen atmosphere tube furnace to prepare the catalyst C1.
The performance indexes of the obtained carrier and the dearsenization agent are detailed in tables 1 and 2, and the acidity characterization of the obtained dearsenization agent is detailed in a figure 1.
Example 2
The embodiment provides a dearsenic agent for hydrogenation of light distillate, which comprises the following components in percentage by mass: NiO 12%, TiO225 percent of MgO 1 percent, C8 percent and the balance of gamma Al2O3；
Wherein the carrier in the dearsenization agent is TiO2-γAl2O3The composite carrier comprises NiO as an active component and MgO and C as auxiliaries.
The preparation method comprises the following steps:
(1) respectively weighing 150.3g of titanium sulfate and 794.7g of aluminum nitrate nonahydrate, placing the titanium sulfate and the aluminum nitrate nonahydrate into a big beaker, adding 2L of deionized water for dissolving, slowly dropwise adding ammonia water under the stirring state, adjusting the pH to 8, precipitating and aging for 3h, carrying out reduced pressure suction filtration, repeatedly washing the deionized water, placing the obtained white solid into an oven at 140 ℃ for drying for 3h, placing the oven in a tubular furnace for roasting at 600 ℃ in the air atmosphere to obtain TiO2-γAl2O3Composite powder FT 2.
(2) 100mL of deionized water is weighed by a measuring cylinder and poured into a beaker, and 38.0g of sucrose and 12.7g of Mg (NO) are weighed3)2Adding the mixture, stirring for 20min until the mixture is fully dissolved, uniformly mixing, and metering to 150 mL. Adding the solution into mixed powder FT2, kneading, extruding to obtain 1.6 mm-diameter wet strip, drying at 120 deg.C for 3 hr, and roasting at 800 deg.C under argon atmosphere for 8 hr to obtain TiO containing Mg and carbon2-γAl2O3The binary composite carrier, namely the hydrogenation dearsenization agent carrier, is recorded as ZT 2.
(3) 93.4g of nickel nitrate hexahydrate is weighed and added into 90mL of deionized water until metal salt is completely dissolved, the volume is determined to be 100mL, 176g of carrier ZT2 is soaked in the solution in the same volume, then the carrier ZT2 is dried for 5h at 140 ℃, and the carrier ZT2 is roasted for 5h at 600 ℃ in an argon atmosphere tube furnace to obtain the catalyst C2.
The performance indexes of the obtained carrier and dearsenization agent are detailed in tables 1 and 2.
Example 3
This embodiment provides aThe dearsenization agent for the hydrogenation of light distillate oil comprises the following components in percentage by mass: NiO 10%, TiO235%, MgO 1.5%, C12%, and the balance of gamma Al2O3；
Wherein the carrier in the dearsenization agent is TiO2-γAl2O3The composite carrier comprises NiO as an active component and MgO and C as auxiliaries.
The preparation method comprises the following steps:
(1) 210.4g of titanium sulfate is weighed and placed in 500mL of deionized water, stirred and dissolved, 83g of gamma-Al is obtained after pseudo-boehmite powder is roasted at 580 DEG C2O3Adding the mixture into a titanium sulfate solution, slowly dropwise adding ammonia water under the stirring state, adjusting the pH value to 8, precipitating and aging for 3 hours, filtering by vacuum filtration, repeatedly washing by deionized water, placing the obtained white solid in a 120 ℃ drying oven for 3 hours, placing in a tubular furnace for roasting at the air atmosphere of 580 ℃ to obtain TiO2-γAl2O3The composite powder was designated as mixed powder FT 3.
(2) 120mL of deionized water was measured by a measuring cylinder and added to the beaker, and 60.0g of glucose and 19.1g of Mg (NO) were further measured3)2Adding the mixture, stirring for 20min, dissolving completely, mixing uniformly, and metering to 150 mL. Adding the solution into mixed powder FT1 for 3 times, kneading, extruding into 1.6 mm-diameter clover-shaped wet strips, drying at 110 deg.C for 5 hr, and roasting at 650 deg.C under nitrogen atmosphere for 4 hr to obtain TiO containing Mg and carbon2-Al2O3The binary composite carrier, namely the hydrogenation dearsenization agent carrier, is recorded as ZT 3.
(3) 77.8g of nickel nitrate hexahydrate is weighed and added into 70mL of deionized water, the mixture is stirred until metal salts are completely dissolved, the volume is determined to be 90mL, 180g of carrier ZT1 is soaked in the solution in the same volume, then the carrier ZT1 is dried for 3h at 120 ℃, and the catalyst C3 is prepared by roasting in a nitrogen atmosphere tube furnace for 3h at 450 ℃.
The performance indexes of the obtained carrier and dearsenization agent are detailed in tables 1 and 2.
Comparative example 1
The only difference from example 1 was that no magnesium source (magnesium nitrate) was added during the preparation, and catalyst D1 was obtained. The performance indexes of the obtained carrier and the dearsenization agent are detailed in tables 1 and 2, and the acidity characterization of the obtained dearsenization agent is detailed in a figure 1.
Comparative example 2
The only difference from example 1 was that no glucose was added, and catalyst D2 was obtained. The performance indexes of the obtained carrier and dearsenization agent are detailed in tables 1 and 2.
The activity of the catalysts obtained in the evaluation examples and the comparative examples of the light distillate containing arsenic, including naphtha and catalytic gasoline, is adopted, and the externally doped arsenic source is triphenyl arsenic. The test is carried out on a 300mL continuous isothermal fixed bed hydrogenation pilot test device, inert ceramic ball particles are filled at the top and the bottom of the reactor, the uniform distribution of material flow is ensured, a dearsenic agent bed layer is supported, and a dearsenic agent is filled in a constant-temperature section of the reactor. The test hydrogen is high-purity hydrogen obtained by high-pressure deoxidation and molecular sieve dehydration, and a process flow of once-through hydrogen is adopted. The dearsenization agent needs to be pre-vulcanized, the dearsenization agent is dried and wet-vulcanized by taking hydrogen as a medium, the vulcanized oil is prepared by adding 2.5 wt% of DMDS into straight-run naphtha, after the air tightness of the device is qualified, the temperature is raised to 150 ℃ at the heating rate of 20 ℃/h, the temperature is kept for 2h, then the vulcanized oil is vulcanized, after the constant temperature is kept for 4h, the temperature is raised to 230 ℃ at 20 ℃/h, the constant temperature is vulcanized for 4h, the temperature is raised to 260 ℃ at 20 ℃/h, the constant temperature is vulcanized for 3h, and after the temperature is raised to 290 ℃ at 20 ℃/h, the vulcanization is finished after the constant temperature is 3.5 h. The experimental conditions are that the reaction temperature is 300 ℃, the pressure is 2.5MPa, and the liquid hourly volume space velocity is 50h-1The hydrogen-oil volume ratio (hydrogen/feed oil) was 100: 1. The dearsenification and desulfurization performance of naphtha is detailed in table 3, and the dearsenification and desulfurization performance of catalytic gasoline is detailed in table 4.
The effective arsenic capacity of the dearsenization agent is measured under the condition of high arsenic, namely an accelerated arsenic capacity test. In addition to arsenic contained in raw oil, arsenic-containing substances are required to be added, so that the arsenic content in the raw oil reaches more than 100 mu g/g, which is more than one hundred times of the arsenic content in industrial raw oil, the arsenic removal performance of the arsenic removal agent is examined, when the arsenic removal rate is lower than 90%, oil feeding is stopped, and the actual arsenic content on the catalyst at the moment is analyzed, namely the arsenic removal capacity of the arsenic removal agent. In the test, triphenylarsenic is used as an externally-doped arsenic source, and the arsenic removal agent in the example 1 is investigated in an arsenic capacity test under the arsenic capacity test conditions of the reaction temperature of 280 ℃, the pressure of 2.5MPa and the liquid hourly volume space velocity of 10h-1The volume ratio of hydrogen to oil (hydrogen/feed oil) was 100:1. As content results are detailed in Table 5
TABLE 1 Performance index of dearsenization agent carrier in examples and comparative examples
TABLE 2 Performance index for dearsenification Agents in examples and comparative examples
TABLE 3 dearsenification and desulfurization indexes for dearsenification agent in naphtha
TABLE 4 Dearsenicating and desulfurization indexes of dearsenification agent in catalytic gasoline
TABLE 5 arsenic Capacity results for the dearsenizing agent of example 1
| Sample numbering | As/μg·kg-1 | Dearsenification/% |
| |
200 | / |
| 30h product | 0.70 | 99.65 |
| 60h product | 0.92 | 98.92 |
| 90h product | 1.13 | 99.44 |
| 120h product | 2.59 | 98.70 |
| 150h product | 21.60 | 89.2 |
Generally speaking, according to NH3NH in TPD spectrum3The desorption temperature can be divided into three types of acid center strength, namely weak acid (100-250 ℃), medium strong acid (250-400 ℃) and strong acid (400 ℃), and as can be seen from figure 1, compared with the dearsenization agent without magnesium (example 1), the signal peak of the dearsenization agent containing magnesium is shifted to the weak acid region, and the peak shape area is reduced, which indicates that the acidity is reduced.
The results of the above examples and comparative examples show that the catalyst prepared by the method of the present invention is used for dearsenization of light distillate oil under typical process conditions, especially under high space velocity conditions, the dearsenization rate is greater than 99%, and the dearsenization agent can effectively ensure that the bromine index of the raw oil is relatively stable, thereby avoiding olefin polymerization scorching, and in addition, the dearsenization agent has a certain desulfurization and denitrification effect, and can be used in combination with a hydrorefining catalyst. In addition, the introduction of the auxiliary agent carbon increases the pore volume of the dearsenization agent, thereby improving the arsenic volume of the dearsenization agent, wherein the arsenic volume is more than 5 wt%, and ensuring the long-term application of the catalyst.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The dearsenization agent for hydrogenation of light distillate oil is characterized by comprising the following components in percentage by mass: NiO 5-20%, TiO210-35%, MgO 0.5-2.5%, C7-14%, and the balance of gamma Al2O3；
Wherein the carrier in the dearsenization agent is TiO2-γAl2O3The composite carrier comprises NiO as an active component and MgO and C as auxiliaries.
2. The dearsenic agent as claimed in claim 1, wherein the dearsenic agent comprises, in mass percent: NiO 8-16%, TiO215-35%, MgO 1-1.5%, C8-12%, and the balance of gamma Al2O3。
3. The method of claim 1 or 2, wherein the method comprises the steps of:
(1) adding TiO into the mixture2-γAl2O3Mixing the composite carrier with the pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier;
(2) and (2) carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and then sequentially carrying out second drying and second roasting to obtain the dearsenic agent.
4. The method according to claim 3, wherein the TiO in the step (1)2-γAl2O3The composite carrier is prepared by a precipitation method, a coprecipitation method or a sol-gel method;
preferably, the specific surface area of the pseudo-boehmite powder is 220-270m2Per g, pore volume of 0.7-1.2cm3(ii)/g, the average pore diameter is 5-25nm, and pores with pore diameters of 4-10nm account for more than 20% of all pores;
preferably, the titanium source in the preparation process of the composite carrier in the step (1) comprises 1 or a combination of at least 2 of titanium sulfate, titanium nitrate, titanium acetate or titanium trichloride, and is preferably titanium sulfate;
preferably, the titanium source and the gamma Al are generated during the preparation process of the composite carrier in the step (1)2O3The mass ratio is (0.74-1.73) to 1.
5. The method according to any one of claims 3 or 4, wherein the pretreatment liquid in step (1) is an aqueous solution of a water-soluble organic substance and a magnesium salt;
preferably, the water-soluble organic substance comprises 1 or a combination of at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid, acetic acid, preferably glucose and/or sucrose;
preferably, the amount of the water-soluble organic substance added to the pretreatment liquid in the step (1) is the amount of the TiO calculated by carbon element2-γAl2O39.6-17% of the composite carrier by mass;
preferably, the magnesium salt comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium sulfate, magnesium acetate, basic magnesium carbonate or magnesium chloride;
preferably, in the pretreatment liquid in the step (1), the amount of the magnesium salt added is in terms of magnesium oxide to the TiO2-γAl2O31.2-2.1% of the composite carrier.
6. The method according to any one of claims 3 to 5, wherein the TiO is mixed in the step (1)2-γAl2O3The solid-liquid ratio g/mL of the composite carrier to the pretreatment liquid is 1 (0.8-0.9).
7. The method according to any one of claims 3 to 6, wherein the temperature of the first drying in step (1) is 100 ℃ to 150 ℃;
preferably, the first drying time in the step (1) is 3-6 h;
preferably, the first firing of step (1) is performed under a protective atmosphere comprising nitrogen or an inert gas;
preferably, the temperature of the first roasting in the step (1) is 500-;
preferably, the time of the first roasting in the step (1) is 4-8 h.
8. The method according to any one of claims 3 to 7, wherein the nickel salt in the nickel salt solution of step (2) comprises 1 or a combination of at least 2 of nickel nitrate, nickel hydroxycarbonate, nickel acetate and nickel citrate, preferably nickel nitrate;
preferably, the content of nickel in the nickel salt solution in the step (2) is 9.5-10.23% by mass;
preferably, the solid-to-liquid ratio of the carrier and the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15): 1;
preferably, the temperature of the second drying in the step (2) is 110-140 ℃;
preferably, the second drying time in the step (2) is 2-5 h;
preferably, the second firing of step (2) is performed under a protective atmosphere comprising nitrogen or an inert gas;
preferably, the temperature of the second roasting in the step (2) is 400-600 ℃;
preferably, the time of the second roasting in the step (2) is 3-6 h.
9. The method of any one of claims 3 to 8, comprising the steps of:
(1) adding TiO into the mixture2-γAl2O3Mixing the composite carrier with the pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier;
(2) carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and then sequentially carrying out second drying and second roasting to obtain the dearsenic agent;
the pretreatment liquid in the step (1) is a water solution of water-soluble organic matters and magnesium salts; the water-soluble organic matter comprises 1 or at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid and acetic acid; in the mixing, the TiO2-γAl2O3The solid-liquid ratio g/mL of the composite carrier to the pretreatment liquid is 1 (0.8-0.9); the first roasting is carried out in a protective atmosphere, wherein the protective atmosphere comprises nitrogen or inert gas; the temperature of the first roasting is 500-800 ℃; the first roasting time is 4-8 h;
the solid-to-liquid ratio of the carrier to the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15): 1; the second roasting is carried out under a protective atmosphere, wherein the protective atmosphere comprises nitrogen or inert gas; the temperature of the second roasting is 400-600 ℃; the time of the second roasting is 3-6 h.
10. The use of the dearsenization agent according to claim 1 or 2, wherein the dearsenization agent is used for dearsenization in hydrogenation of light distillate oil, and the dearsenization agent is subjected to a sulfurization treatment before use.
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