CN106925249B - Zinc oxide desulfurizer containing zinc-aluminum spinel - Google Patents
Zinc oxide desulfurizer containing zinc-aluminum spinel Download PDFInfo
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- CN106925249B CN106925249B CN201511021113.0A CN201511021113A CN106925249B CN 106925249 B CN106925249 B CN 106925249B CN 201511021113 A CN201511021113 A CN 201511021113A CN 106925249 B CN106925249 B CN 106925249B
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- zinc
- aluminum
- containing solution
- zinc oxide
- solution
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 72
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 35
- 239000011029 spinel Substances 0.000 title claims abstract description 35
- 229910000611 Zinc aluminium Inorganic materials 0.000 title claims description 18
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 97
- 239000011701 zinc Substances 0.000 claims abstract description 97
- -1 zinc aluminate Chemical class 0.000 claims abstract description 24
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 75
- 229910052782 aluminium Inorganic materials 0.000 claims description 72
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 70
- 239000000463 material Substances 0.000 claims description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- 229910001868 water Inorganic materials 0.000 claims description 29
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 238000004448 titration Methods 0.000 claims description 16
- 230000003009 desulfurizing effect Effects 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 229910052750 molybdenum Chemical class 0.000 claims description 2
- 239000011733 molybdenum Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 12
- 230000023556 desulfurization Effects 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 130
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000203 mixture Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 9
- 229940078494 nickel acetate Drugs 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000002872 contrast media Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-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
- 229930006000 Sucrose Natural products 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a zinc oxide desulfurizer containing zinc aluminate spinel, which comprises 30-80 wt% of zinc oxide, 10-20wt% of nickel oxide, 0-10wt% of molybdenum oxide and 150-220m of catalyst specific surface area2(ii) in terms of/g. When the desulfurizer is applied to desulfurization treatment of catalytic gasoline, the loss of octane number is small.
Description
Technical Field
The invention relates to a zinc oxide desulfurizer containing zinc aluminate spinel and a preparation method thereof, and the catalyst is suitable for desulfurization purification technology, in particular for desulfurization treatment of catalytic cracking gasoline.
Background
The composite material of zinc oxide and aluminum oxide is often used as a desulfurization catalytic material in the technical field of adsorption desulfurization. Common methods for preparing the material at present include impregnation, mechanical mixing, coprecipitation, and peptization. The impregnation method and the mechanical mixing method use the aluminum oxide material as a precursor, and the specific surface area of the aluminum oxide material is adjusted, so that the composite material with higher specific surface area can be prepared by the two methods, but the aluminum oxide and the zinc oxide in the composite material have weaker interaction, so that the zinc oxide is easy to lose in the using process, and the zinc oxide is prevented from losing by promoting the two methods to form spinel by adopting a high-temperature roasting method; the coprecipitation method and the peptization method adopt compounds containing aluminum and zinc to prepare a zinc-aluminum precursor through precipitation or peptization, the aluminum and the zinc generate stronger interaction through reaction in the preparation process so as to avoid zinc oxide loss in the use process, but the specific surface area of the materials prepared by the peptization method is the lowest, so that the materials are restricted when being used as desulfurization materials.
US5525210 discloses a process for desulfurizing FCC gasoline, the main active component of which is L acid such as zinc oxide supported on alumina carrier, by impregnation and coprecipitation, wherein the impregnation produces a material with a specific surface area of 142m after calcination at 815 deg.C2(g), the specific surface area of the material prepared by the coprecipitation method is 74m after the material is roasted at 704 DEG C2(ii) in terms of/g. The two methods have higher roasting temperature and lower specific surface area of the prepared zinc-aluminum material.
CN200710045746.4 discloses a catalytic cracking assistant capable of reducing the sulfur content of gasoline, which contains zinc-aluminum spinel, uniformly dispersed zinc oxide and at least one optional rare earth metal oxide composite oxide, and is prepared by roasting a mixture of zinc-aluminum layered substance with hydrotalcite-like structure and optional rare earth hydrated oxide, and the chemical formula of the mixture is ZnAl2O4·(1-9)ZnO·(0-0.5)RE2O3(ii) a The preparation method is that sodium hydroxide and soluble inorganic sodium salt are dripped into the mixed solution of zinc salt, aluminum salt and rare earth ions, the pH value of the solution is 8-11, and the solution is roasted for 1-4h at the temperature of 500-1000 ℃. The formed auxiliary agent is blended with a conventional FCC catalyst and/or an activity strengthening auxiliary agent and applied to a catalytic cracking process, has the function of reducing the sulfur content of gasoline and has excellent hydrothermal stability. In order to obtain a zinc-aluminium spinel structure, the material needs to be roasted at a higher temperature, and the specific surface area after roasting is 120m at most2/g。
CN201210178395.5 discloses a preparation method of nano zinc-aluminum spinel, which comprises the steps of adding zinc salt into water for dissolving, adding an aluminum source, stirring for 10-30 minutes, adding a pore-expanding agent, stirring, aging for 30-60 minutes at 20-100 ℃, drying, and roasting at 500-1200 ℃; the molar ratio of the raw materials is Zn, Al and water is 1: 2: 16-35; the addition amount of the pore-expanding agent is 0.5-30% calculated by taking the mass of the zinc oxide as 100%; the pore-enlarging agent is one or more of sucrose, glycerol, ammonium carbonate, ammonium bicarbonate, polystyrene emulsion and polyethylene glycol. The specific surface area of the synthesized zinc-aluminum spinel is from 60 to 300m2(ii) in terms of/g. The zinc-aluminum mixture ratio of the material fed by the method is low, and the pore-expanding agent is added in the preparation process, so that only the zinc-aluminum spinel is obtained, and the zinc-aluminum spinel does not contain uniformly dispersed zinc oxide.
CN201310625314.6 discloses a preparation method of a photocatalytic material with strong adsorption and high visible light degradation performance, and the invention relates to a zinc aluminum spinel with a high specific surface mesoporous structure, zinc oxide and nickel oxide nano composite photocatalytic material obtained by using ternary hydrotalcite as a precursor through high-temperature roasting, and a preparation method thereof. Zinc nitrate, nickel nitrate, aluminum nitrate, sodium carbonate, sodium hydroxide and the like are used as raw materials to be prepared into a salt solution and an alkali solution respectively, and the salt solution and the alkali solution are mixed by a constant flow pump under the magnetic stirring at the temperature of 80 ℃; transferring the reaction mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal treatment for 5-10h at the temperature of 130-; filtering, washing and drying to obtain a precursor, putting the precursor into a muffle furnace to roast for 2-6 hours at the temperature of 400-600 ℃ to obtain a product, wherein the molar ratio of zinc ions to nickel ions to aluminum ions is1-3:1-3:1-3, and the specific surface area is more than 150m2(ii) in terms of/g. The method needs hydrothermal treatment in the process of synthesizing the ternary hydrotalcite-like precursor, and the treatment time is long.
CN200310121344.X discloses a preparation method of aluminum-doped nano-grade zinc oxide conductive powder. The method is characterized in that a mixed salt solution of soluble salts of zinc, doped elements of aluminum, gallium, indium, yttrium, scandium, tin, germanium and silicon and a precipitator are simultaneously dripped into water, coprecipitation is generated under the conditions of controlling the temperature of the whole reaction system to be 40-75 ℃ and the pH value to be 7.0-7.5 to generate doped zinc oxide precursor basic zinc carbonate, and the doped superfine zinc oxide conductive powder material is prepared by roasting in the mixed atmosphere of hydrogen and argon, but the material prepared by the method is applied to a conductive material, and the adding molar quantity of the doped elements is only 0.1-10% of the total molar quantity of zinc and the doped elements.
CN200510028233.3 discloses a method for preparing a catalytic cracking flue gas high-efficiency sulfur transfer agent, which comprises the steps of dropwise adding a mixed solution of zinc salt, magnesium salt, aluminum salt and cerium salt into a mixed solution of sodium hydroxide and sodium carbonate by taking zinc, magnesium and aluminum as active components and cerium and vanadium as auxiliaries at the temperature of 60-80 ℃ and the pH value of 8-10, roasting the obtained coprecipitation product at the temperature of 400-80 ℃ for 6-8h, and preparing zinc-magnesium-aluminum-cerium hydrotalcite by a coprecipitation method, wherein the molar ratio of the three metals of zinc, magnesium and aluminum is 1.0:1.0-4.5:1.0-2.0, and the sulfur transfer agent prepared by adopting the material has high-efficiency SOx adsorption and desorption performances and good mechanical strength.
CN200910087590.5 discloses a desulfurizing agent for reforming raw oil and a preparation method thereof, the preparation method of the catalyst relates to a blending method, a eutectic method and a coprecipitation method, and is characterized in that the desulfurizing agent comprises the following components by weight: ZnO: 10% -40%, NiO: 15% -22% of Al2O3：10％-17％、SiO2: 5% -22%, the balance being unavoidable impurities.
CN201310089762.9 discloses a nano-sized layered composite hydroxide and a fractional precipitation preparation method thereof, which adopts soluble salt and alkali of metal as raw materials to respectively precipitate metal ions forming an LDH laminate through fractional precipitation reactionAnd producing LDH with a specific surface area of 140-280m in the second precipitation step2(ii) in terms of/g. Compared with a coprecipitation method, the method adopts twice precipitation, but the prepared LDH material has higher specific surface area, but the reaction time is longer, and the reaction time given in the examples is more than 10 hours.
Research on auxiliary agents for reducing sulfur content of catalytically cracked gasoline, namely synthesis of zinc aluminate spinel and cracking desulfurization performance of zinc aluminate spinel (author: Wangpo; China petrochemical Co., Ltd., (Petroleum institute) (2003-19 vol 2)): discloses a preparation method of zinc aluminate spinel: mixing sodium metaaluminate solution and zinc nitrate solution according to m (Al)2O3) And m (ZnO) 9, adding dropwise into distilled water at 40 ℃ at the same rate, mixing uniformly, adding 16% sodium hydroxide solution, adjusting the pH value of the solution to 8.6, aging the generated precipitate for 15min, adding a small amount of sodium hydroxide solution, and adjusting the pH value to 9.0. Filtering and washing the precipitate for more than 3 times to remove Na+. Finally, the precipitate is dried at 120 ℃ for 4h and then calcined at 700 ℃ for 2 h. The specific surface area of the sample is basically 160m2And about/g.
Disclosure of Invention
The invention aims to provide a zinc oxide desulfurizer containing zinc aluminate spinel with higher desulfurization rate and penetrating sulfur capacity, and the desulfurizer has smaller octane value loss when being applied to desulfurization treatment of catalytic gasoline.
The technical problem to be solved by the invention is to prepare a zinc-aluminum hydrotalcite-like structure layered material by alternately titrating an aluminum-containing sodium carbonate solution and a zinc-containing solution under the condition of non-constant pH value, obtain a uniformly dispersed zinc oxide material containing zinc-aluminum spinel after roasting at a lower temperature, and prepare a high-activity and high-selectivity catalytic cracking gasoline desulfurizer after loading active metals by an impregnation method. The zinc oxide and the aluminum oxide in the desulfurizer interact in a spinel form, can be directly molded without additionally providing a binder, has high strength and large specific surface area, and solves the problems of low strength and low specific surface area and limited use of the conventional preparation method for preparing the zinc oxide-containing material.
The zinc oxide desulfurizer containing zinc aluminate spinel disclosed by the invention comprises 30-80 wt% of zinc oxide, 10-20wt% of nickel oxide and 0-10wt% of molybdenum oxide in terms of oxides. The content of zinc oxide is preferably 40 to 80wt%, and the content of zinc oxide is more preferably 45 to 75 wt%; the specific surface area of the catalyst is 150-220m2The specific surface area is preferably 180-220m2A specific surface area of 200-220m is more preferable2(ii) in terms of/g. When the content of the zinc oxide is controlled to be 40-80wt%, the specific surface area of the catalyst is 180-220m2(ii)/g; when the content of the zinc oxide is controlled to be 45-75wt%, the specific surface area of the catalyst is 200-220m2(ii) in terms of/g. The amount of zinc oxide according to the invention may vary from 30 to 80wt%, such as from 30 to 50 wt%, from 55 to 80wt%, from 50 to 70 wt%, from 60 to 70 wt%.
The invention provides a preparation method of a zinc oxide desulfurizer containing zinc aluminate spinel, which comprises the following steps:
1) dissolving soluble zinc salt in water to obtain a zinc-containing solution;
2) dissolving sodium metaaluminate and sodium carbonate in water to obtain an aluminum-containing solution;
3) dividing the zinc-containing solution in the feeding amount in the step 1) into 2-4 parts, taking one part of the zinc-containing solution, dropwise adding the aluminum-containing solution in the step 2) at 40-80 ℃, and stopping dropwise adding the aluminum-containing solution when the pH value reaches 8.5-9.5; dripping one part of zinc-containing solution into the mixing system; continuously dripping the aluminum-containing solution after the part of the zinc-containing solution is completely dripped, and stopping dripping the aluminum-containing solution when the pH value reaches 8.5-9.5; and (3) titrating the aluminum-containing solution and the zinc-containing solution alternately according to the method until the zinc-containing solution with the feeding amount is completely dripped into the mixing system, dripping the aluminum-containing solution for the last time, and finishing the alternate titration process of the non-constant pH value when the pH value reaches 8.5-9.5. Controlling the titration speed to be 0.5-6 h;
4) aging at 75-95 deg.C for 2-8h, cooling and washing to neutrality, drying at 80-140 deg.C in air atmosphere for 4-10h, and calcining at 550 deg.C for 4-10h to obtain zinc oxide material containing zinc aluminate spinel.
5) Kneading and molding the zinc oxide material, preparing a solution by using soluble salts of nickel and molybdenum for impregnation, drying the solution for 4 to 10 hours at the temperature of between 80 and 140 ℃ in an air atmosphere, and roasting the solution for 4 to 10 hours at the temperature of between 450 and 550 ℃ to obtain the desulfurizer.
The soluble zinc salt can be one or more of zinc nitrate, zinc acetate and zinc chloride.
The zinc oxide desulfurizer containing zinc aluminate spinel is used for catalytic cracking gasoline desulfurization, and the reaction process conditions are as follows: the reaction temperature is 300-- 1The volume ratio of hydrogen to oil is 0.2-0.4.
Compared with the prior art, the zinc oxide desulfurizer containing zinc-aluminum spinel is prepared by non-constant pH alternate titration, namely, aluminum-containing sodium carbonate solution and zinc-containing solution are alternately titrated under the condition of non-constant pH value, so that the zinc-containing solution is required to be divided into 2-4 parts. The aluminum-containing sodium carbonate solution is a strong alkaline solution, the zinc-containing strong acid weak base salt solution is an acidic solution, and multiple alternate titrations between the aluminum and zinc solutions enable the pH value to swing between acid and alkali, so that the aluminum and zinc precursors can be orderly stacked into a layered structure, and the aluminum and zinc precursors can be directly roasted and formed at low temperature to be uniformly dispersed, have high strength and the specific surface area of 150-220m2The specific surface area of the zinc oxide desulfurizer containing the zinc aluminate spinel regulated and controlled between/g can be, for example, 180-200m2/g，160-210m2/g，200-220m2The concentration is in the same range as the concentration of the zinc oxide, the problem that a precursor obtained by titrating the zinc-aluminum mixed solution by adopting an alkaline solution in one step needs to be roasted at a high temperature to fix the zinc oxide is solved, and the hydrothermal treatment process is also reduced. The desulfurizer has larger strength and specific surface area, and the specific surface area can be 150-220m2The specific surface area can be controlled between 180 and 200m2/g，160-210m2/g，155-175m2/g，200-220m2(ii) in terms of/g. It is suitable for the desulfurization treatment of the catalytic gasoline.
Drawings
FIG. 1 is an XRD representation of zinc oxide desulfurization agents 1-6 comprising zinc aluminate spinels prepared in examples 1-6. The XRD spectrums of the samples 1-6 contain XRD characteristic peaks of two phases of zinc aluminate spinel and zinc oxide, which indicates that the desulfurizer 1-6 is a zinc oxide material containing zinc aluminate spinel.
Detailed Description
The main raw material sources for preparing the catalyst are as follows:
the raw material reagents used in the invention are all commercial products.
Analytical methods and standards:
analyzing the sulfur content of the oil product: SH/T0689-
The properties of the gasoline raw material are as follows: the Lanzhou petrochemical gasoline is used as a raw material, the sulfur content is 300mg/kg, the RON is 91.5, and the olefin content is 40 v%.
Example 1
800g of zinc nitrate is dissolved in 4L of water to prepare a zinc-containing solution, and 120g of sodium metaaluminate and 120g of sodium carbonate are dissolved in 1.7L of water to prepare an aluminum-containing solution. And (3) taking 2L of zinc-containing solution, controlling the temperature of the system to be 60 ℃, dropwise adding an aluminum-containing solution into the zinc-containing solution until the pH value reaches 9, stopping dropwise adding the aluminum-containing solution, dropwise adding the rest 2L of zinc-containing solution into the mixing system, continuously dropwise adding the aluminum-containing solution until the pH value reaches 9, and keeping the titration time for 4 hours. The resulting mixture was aged at 85 ℃ for 4h, cooled and washed to neutrality, and dried at 120 ℃ for 5h in an air atmosphere.
Extruding and molding the dried material, and roasting at 500 ℃ for 6 hours; 60.55g of ammonium molybdate and 226.25g of nickel acetate are dissolved in 350mL of ammonia water to prepare a steeping liquor, 500g of roasted material is soaked in the steeping liquor, the soaked material is dried for 5 hours in the air atmosphere at 120 ℃, and the roasted material is roasted for 6 hours at 500 ℃ to obtain the desulfurizer 1, wherein the content of zinc oxide is 50 wt%, and the specific surface area is 210m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Comparative example 1
Dissolving 800g of zinc nitrate and 550g of zinc nitrate in 4L of water to prepare a zinc-containing and aluminum-containing solution; 120g of sodium carbonate was dissolved in 1.7L of water to prepare a sodium carbonate solution. Controlling the temperature of the system to be 60 ℃, and dropwise adding a zinc-containing and aluminum-containing solution into the sodium carbonate solution until the pH value reaches 9. The resulting mixture was aged at 85 ℃ for 4h, cooled and washed to neutrality, and dried at 120 ℃ for 5h in an air atmosphere.
Extruding and molding the dried material, and roasting at 500 ℃ for 6 hours; 60.55g of ammonium molybdate and 226.25g of nickel acetate are dissolved in 350mL of ammonia water to prepare a steeping liquor, 500g of roasted material is soaked in the steeping liquor, the roasted material is dried for 5 hours at 120 ℃ in an air atmosphere, and the roasted material is roasted at 500 DEG C6h, obtaining a contrast agent 1, wherein the content of the zinc oxide is 50 wt%, and the specific surface area is 110m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Compared with the comparative example 1, the sodium carbonate and the aluminum are prepared into a mixed solution and then are titrated alternately with the zinc-containing solution in the example 1, so that the desulfurizing agent with the same zinc oxide content is obtained, but the specific surface area of the example 1 is higher.
Example 2
1.6kg of zinc nitrate is dissolved in 8L of water to prepare a zinc-containing solution, and 0.11kg of sodium metaaluminate and 0.38kg of sodium carbonate are dissolved in 3.4L of water to prepare an aluminum-containing solution. The zinc containing solution was divided equally into 4 portions of 2L each. Taking 2L of zinc-containing solution, controlling the temperature of the system to be 75 ℃, and dropwise adding an aluminum-containing solution into the zinc-containing solution until the pH value reaches 8.7; stopping dripping the aluminum-containing solution, dripping 2L of zinc-containing solution into the mixing system, and continuously dripping the aluminum-containing solution until the pH value reaches 8.7; and (3) alternately titrating the aluminum-containing solution and the zinc-containing solution until the zinc-containing solution is completely added into the mixing system, and finally dropwise adding the aluminum-containing solution until the pH value reaches 8.7, wherein the titration time is 6 hours in total. The resulting mixture was aged at 90 ℃ for 6 hours, then cooled and washed to neutrality, and dried at 110 ℃ for 6 hours in an air atmosphere.
Extruding and molding the dried material, and roasting at 540 ℃ for 8 h; 0.74kg of nickel nitrate is dissolved in 0.75L of deionized water to prepare an impregnation solution to impregnate 1kg of roasted material, the impregnated material is dried for 6h in the air atmosphere at the temperature of 110 ℃, and the impregnated material is roasted for 8h at the temperature of 540 ℃ to obtain a desulfurizing agent 2, the content of zinc oxide is 70 wt%, and the specific surface area is 162m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Comparative example 2
1.6kg of zinc nitrate is dissolved in 8L of water to prepare a zinc-containing solution, and 0.11kg of sodium metaaluminate and 0.38kg of sodium carbonate are dissolved in 3.4L of water to prepare an aluminum-containing solution. And controlling the temperature of the system to be 75 ℃, dropwise adding an aluminum-containing solution into the zinc-containing solution until the pH value reaches 8.7, and the titration time is 6 hours in total. The resulting mixture was aged at 90 ℃ for 6 hours, then cooled and washed to neutrality, and dried at 110 ℃ for 6 hours in an air atmosphere.
Extruding and molding the dried material, and roasting at 540 ℃ for 8 h; dissolving 0.74kg of nickel nitrate in 0.75L of deionized water to prepare a soaking solution, soaking 1kg of roasted material, drying for 6h in an air atmosphere at 110 ℃, and roasting at 540 DEG C8h to obtain contrast agent 2, the content of zinc oxide is 70 wt%, and the specific surface area is 120m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Compared with the comparative example 2, the alternative titration of zinc and aluminum solution adopted in the example 2 can obtain the desulfurizing agent with the same zinc oxide content, but the specific surface area of the example 2 is higher.
Example 3
296g of zinc acetate is dissolved in 2L of water to prepare a zinc-containing solution, and 47g of sodium metaaluminate and 74g of sodium carbonate are dissolved in 0.85L of water to prepare an aluminum-containing solution. The zinc containing solution was divided equally into 3 portions of 0.67L each. Taking 0.67L of zinc-containing solution, controlling the temperature of the system to be 55 ℃, and dropwise adding an aluminum-containing solution into the zinc-containing solution until the pH value reaches 9.3; stopping dripping the aluminum-containing solution, dripping 0.67L of zinc-containing solution into the mixing system, and continuously dripping the aluminum-containing solution until the pH value reaches 9.3; stopping dripping the aluminum-containing solution, dripping 0.67L of zinc-containing solution into the mixing system, and finally dripping the aluminum-containing solution until the pH value reaches 9.3, wherein the titration time is 3 hours in total. The resulting mixture was aged at 80 ℃ for 7h, cooled and washed to neutrality, and dried at 100 ℃ for 8h in an air atmosphere.
Extruding and molding the dried material, and roasting at 490 ℃ for 9 h; 3.02g of ammonium molybdate and 61.70g of nickel acetate are dissolved in 80mL of ammonia water to prepare a steeping liquor, 100g of roasted material is soaked in the steeping liquor, the soaked material is dried for 8 hours in an air atmosphere at 100 ℃, and the roasted material is roasted for 9 hours at 490 ℃, so that a desulfurizing agent 3 is obtained, the content of zinc oxide is 58 wt%, and the specific surface area is 200m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Comparative example 3
Dissolving 296g of zinc acetate and 215g of sodium metaaluminate in 2L of water to prepare a zinc-containing and aluminum-containing solution; a sodium carbonate solution was prepared by dissolving 74g of sodium carbonate in 0.85L of water. Controlling the temperature of the system to be 55 ℃, dropwise adding a sodium carbonate solution into the zinc-containing and aluminum-containing solution until the pH value reaches 9.3, and the total titration time is 3 hours. The resulting mixture was aged at 80 ℃ for 7h, cooled and washed to neutrality, and dried at 100 ℃ for 8h in an air atmosphere.
Extruding and molding the dried material, and roasting at 490 ℃ for 9 h; dissolving 3.02g of ammonium molybdate and 61.70g of nickel acetate in 80mL of ammonia water to prepare a steeping liquor, steeping 100g of roasted material, drying for 8h in an air atmosphere at 100 ℃, and roasting for 9h at 490 ℃ to obtain the ammonium molybdate/nickel acetate/ammonium molybdate/nickel acetate/cobalt oxide composite materialComparative agent 3, zinc oxide content 58 wt%, specific surface area 165m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
In comparison with example 3, comparative example 3 titrates a mixed solution containing zinc and aluminum with a sodium carbonate solution, and although a desulfurizing agent having the same content of zinc oxide is obtained, comparative example 3 has a lower specific surface area.
Example 4
4kg of zinc nitrate is dissolved in 20L of water to prepare a zinc-containing solution, and 0.34kg of sodium metaaluminate and 0.87kg of sodium carbonate are dissolved in 8.5L of water to prepare an aluminum-containing solution. Taking 10L of zinc-containing solution, controlling the temperature of the system to be 40 ℃, and dropwise adding an aluminum-containing solution into the zinc-containing solution until the pH value reaches 8.9; stopping dripping the aluminum-containing solution, dripping 5L of zinc-containing solution into the mixing system, and continuously dripping the aluminum-containing solution until the pH value reaches 8.9; stopping dripping the aluminum-containing solution, dripping 5L of zinc-containing solution into the mixing system, and finally dripping the aluminum-containing solution until the pH value reaches 8.9, wherein the total titration time is 5.5 h. Aging the obtained mixture at 76 deg.C for 8h, cooling and washing to neutrality, spray rolling ball molding, drying at 120 deg.C in air atmosphere for 4h, and calcining at 510 deg.C for 4 h.
1.21kg of nickel nitrate and 0.1kg of ammonium nitrate are dissolved in 1.4L of deionized water to prepare an impregnation solution, 2kg of roasted material is impregnated in the impregnation solution, the impregnated material is dried for 4 hours at 120 ℃ in the air atmosphere and roasted for 4 hours at 510 ℃ to obtain a desulfurizer 4, the content of zinc oxide is 71 wt%, and the specific surface area is 198m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Comparative example 4
Dissolving 4kg of zinc nitrate in 20L of water to prepare a zinc-containing solution, dissolving 0.34kg of sodium metaaluminate in 8.5L of water to prepare an aluminum-containing solution, dripping the two solutions into distilled water at 40 ℃ at the same speed, uniformly mixing, then adding a 16% sodium hydroxide solution, adjusting the pH value of the solution to 8.6, aging the generated precipitate for 15min, then adding a small amount of sodium hydroxide solution, adjusting the pH value to 9.0, and the total titration time is 5.5 h. The resulting mixture was cooled and washed to neutrality, spray-rolled into a ball, dried at 120 ℃ for 4 hours in an air atmosphere, and calcined at 510 ℃ for 4 hours.
1.21kg of nickel nitrate and 0.1kg of ammonium nitrate are dissolved in 1.4L of deionized water to prepare a steeping liquor for steeping2kg of the calcined substance, dried at 120 ℃ for 4 hours in an air atmosphere, and calcined at 510 ℃ for 4 hours to obtain a contrast agent 4, the content of zinc oxide was 62 wt%, and the specific surface area was 165m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Compared with the embodiment 4, the comparative example 4 adopts the sodium hydroxide solution to titrate the mixture containing zinc and aluminum, and adjusts the pH value of the mixing system from 8.6 to 9.0 through the sodium hydroxide solution, so that the zinc oxide desulfurizer has lower zinc oxide content and lower specific surface area.
Example 5
1.9kg of zinc chloride is dissolved in 20L of water to prepare a zinc-containing solution, and 0.40kg of sodium metaaluminate and 0.80kg of sodium carbonate are dissolved in 8.5L of water to prepare an aluminum-containing solution. Taking 8L of zinc-containing solution, controlling the temperature of the system to be 65 ℃, and dropwise adding an aluminum-containing solution into the zinc-containing solution until the pH value reaches 9.1; the remaining zinc containing solution was aliquoted into 3 portions of 4L each. And (3) alternately titrating the aluminum-containing solution and the zinc-containing solution until the zinc-containing solution is completely added into the mixing system, and finally dropwise adding the aluminum-containing solution until the pH value reaches 9.1 and the titration time is 6 hours in total. The resulting mixture was aged at 76 ℃ for 8h, cooled and washed to neutrality, spray ball-shaped, dried at 90 ℃ for 10h in an air atmosphere, and calcined at 510 ℃ for 9.5 h.
0.70kg of nickel acetate and 0.1kg of triethylene glycol are dissolved in 0.75L of ammonia water to prepare impregnation liquid, 1kg of roasted material is soaked in the impregnation liquid, the impregnation liquid is dried for 10h in an air atmosphere at the temperature of 90 ℃, and the roasting is carried out for 9.5h at the temperature of 510 ℃ to obtain the desulfurizer 5, wherein the content of zinc oxide is 62 wt%, and the specific surface area is 208m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Comparative example 5
Dissolving 1.9kg of zinc chloride in 20L of water to prepare a zinc-containing solution, adjusting the pH value to 6.5 by using 1.0M of sodium hydroxide solution under the condition of stirring, adjusting the pH value to 7.0 by using 0.1-0.2M of ammonia water, standing the precipitate for 24h, filtering, washing the precipitate for several times by using water until no sodium ions exist in the filtrate, pulping a filter cake, spraying and rolling balls, forming, drying for 10h in an air atmosphere at 90 ℃, and roasting for 9.5h at 510 ℃.
0.70kg of nickel acetate and 0.1kg of triethylene glycol are dissolved in 0.75L of ammonia water to prepare a steeping liquor, 1kg of roasted material is soaked in the steeping liquor, the roasted material is dried for 10h in an air atmosphere at the temperature of 90 ℃, the roasted material is roasted for 9.5h at the temperature of 510 ℃,comparative agent 5 was obtained, the content of zinc oxide was 83 wt%, and the specific surface area was 60m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
Compared with example 5, the zinc oxide material prepared in comparative example 5 does not contain zinc aluminate spinel, and has a lower specific surface area.
Example 6
2.4kg of zinc nitrate is dissolved in 12L of water to prepare a zinc-containing solution, and 0.32kg of sodium metaaluminate and 0.40kg of sodium carbonate are dissolved in 5L of water to prepare an aluminum-containing solution. The zinc containing solution was divided equally into 4 portions of 3L each. Taking 3L of zinc-containing solution, controlling the temperature of the system to be 75 ℃, and dropwise adding an aluminum-containing solution into the zinc-containing solution until the pH value reaches 9.4; stopping dripping the aluminum-containing solution, dripping 3L of zinc-containing solution into the mixing system, and continuously dripping the aluminum-containing solution until the pH value reaches 9.4; and (3) alternately titrating the aluminum-containing solution and the zinc-containing solution until the zinc-containing solution is completely added into the mixing system, and finally dropwise adding the aluminum-containing solution until the pH value reaches 9.4, wherein the titration time is 2 hours in total. Aging the obtained mixture at 75 deg.C for 4h, cooling and washing to neutrality, spray rolling ball molding, drying at 130 deg.C in air atmosphere for 2h, and baking at 450 deg.C for 10 h.
0.82kg of nickel acetate and 0.1kg of triethylene glycol are dissolved in a mixed solution of 0.2L of ammonia water and 0.55L of deionized water to prepare an impregnation solution, 1kg of roasted product is impregnated, the roasted product is dried for 2 hours in an air atmosphere at the temperature of 130 ℃, and the roasted product is roasted for 10 hours at the temperature of 450 ℃ to obtain a desulfurizer 6, the content of zinc oxide is 52 wt%, and the specific surface area is 218m2(ii) in terms of/g. The composition and physicochemical properties thereof are shown in Table 1.
The desulfurizing agents 1 to 6 prepared in examples 1 to 6 and the contrast agents 1 to 5 prepared in comparative examples 1 to 5 are respectively filled into a 200ml adiabatic bed reactor, and the gasoline raw material with the sulfur content of 300mg/kg, the olefin content of 40 percent and the RON of 91.5 is subjected to hydrodesulfurization modification, wherein the reaction process conditions are as follows: the reaction temperature is 400 ℃, and the volume space velocity is 3.0h-1The reaction pressure is 2.4MPa, and the volume ratio of hydrogen to oil is 0.3. The reaction results are shown in Table 1.
Claims (6)
1. A zinc-containing compositionThe aluminum spinel zinc oxide desulfurizer is characterized in that the desulfurizer mainly comprises the following components in terms of oxides: 40-80wt% of zinc oxide, 10-20wt% of nickel oxide, 0-10wt% of molybdenum oxide, and the specific surface area of the desulfurizing agent is 150-2The preparation method of the zinc oxide desulfurizer containing zinc aluminate spinel comprises the following steps:
1) dissolving soluble zinc salt in water to obtain a zinc-containing solution; 2) dissolving sodium metaaluminate and sodium carbonate in water to obtain an aluminum-containing solution; 3) dividing the zinc-containing solution in the feeding amount in the step 1) into 2-4 parts, taking one part of the zinc-containing solution, dropwise adding the aluminum-containing solution in the step 2) at 40-80 ℃, and stopping dropwise adding the aluminum-containing solution when the pH value reaches 8.5-9.5 to form a mixing system; dripping one part of zinc-containing solution into the mixing system; continuously dripping the aluminum-containing solution after the zinc-containing solution is completely dripped, and stopping dripping the aluminum-containing solution when the pH value reaches 8.5-9.5; alternately titrating the aluminum-containing solution and the zinc-containing solution according to the method until the zinc-containing solution with the feeding amount is completely dripped into the mixing system, finally dripping the aluminum-containing solution, finishing the alternate titration process of the non-constant pH value when the pH value reaches 8.5-9.5, and controlling the titration speed to be 0.5-6 h; 4) aging at 75-95 deg.C for 2-8h, cooling and washing to neutrality, drying at 80-140 deg.C in air atmosphere for 4-10h, and calcining at 550 deg.C for 4-10h to obtain zinc oxide material containing zinc aluminate spinel; 5) kneading and molding the zinc oxide material, preparing a solution by using soluble salts of nickel and molybdenum for impregnation, drying the solution for 4 to 10 hours at the temperature of between 80 and 140 ℃ in an air atmosphere, and roasting the solution for 4 to 10 hours at the temperature of between 450 and 550 ℃ to obtain the desulfurizer.
2. The zinc oxide desulfurizing agent comprising zinc aluminate spinel according to claim 1, wherein the content of zinc oxide is 45-75 wt%.
3. The zinc oxide desulfurizing agent containing zinc aluminate spinel as claimed in claim 1, wherein the specific surface area of the desulfurizing agent is 180-220m2/g。
4. The zinc aluminum containing spinel of claim 1The zinc oxide desulfurizer is characterized in that the specific surface area of the desulfurizer is 200-220m2/g。
5. The zinc oxide desulfurizing agent containing zinc aluminate spinel as claimed in claim 1, wherein the content of zinc oxide is 45-75wt%, and the specific surface area is 200-220m2/g。
6. The zinc oxide desulfurizing agent containing zinc aluminate spinel according to claim 1, wherein the soluble zinc salt is one or more of zinc nitrate, zinc acetate and zinc chloride.
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