CN106925337B - Hydrodesulfurization modification catalyst and preparation method thereof - Google Patents
Hydrodesulfurization modification catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106925337B CN106925337B CN201511019201.7A CN201511019201A CN106925337B CN 106925337 B CN106925337 B CN 106925337B CN 201511019201 A CN201511019201 A CN 201511019201A CN 106925337 B CN106925337 B CN 106925337B
- Authority
- CN
- China
- Prior art keywords
- zinc
- aluminum
- containing solution
- hydrodesulfurization
- catalyst
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 16
- 230000004048 modification Effects 0.000 title abstract description 16
- 238000012986 modification Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 82
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 60
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002808 molecular sieve Substances 0.000 claims abstract description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004448 titration Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 125
- 239000011701 zinc Substances 0.000 claims description 92
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 83
- 229910052725 zinc Inorganic materials 0.000 claims description 83
- 229910052782 aluminium Inorganic materials 0.000 claims description 76
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 76
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 12
- 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 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004523 catalytic cracking Methods 0.000 abstract description 6
- -1 VIB group metals Chemical class 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 46
- 239000000203 mixture Substances 0.000 description 46
- 238000002156 mixing Methods 0.000 description 25
- 239000011787 zinc oxide Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- 239000011609 ammonium molybdate Substances 0.000 description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 12
- 235000018660 ammonium molybdate Nutrition 0.000 description 12
- 229940010552 ammonium molybdate Drugs 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- 238000000975 co-precipitation Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052596 spinel Inorganic materials 0.000 description 8
- 239000011029 spinel Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 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 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 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 2
- 229910018072 Al 2 O 3 Inorganic materials 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 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
- 238000001914 filtration Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-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
- 230000035484 reaction time Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 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
- 230000009286 beneficial effect 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
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 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
- 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
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment 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
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 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
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 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
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin 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
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- B01J35/61—
-
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
the invention relates to a hydrodesulfurization modification catalyst, which takes the weight of the catalyst as a reference, the content of a molecular sieve is 5-70 wt%, the content of VIB group metals is 2-10 wt% calculated by oxides, the content of VIII group metals is 1-5 wt% calculated by oxides, the zinc-aluminum layered material prepared by non-constant pH alternate titration is 5-50%, and the phosphorus content is 0-10 wt% calculated by oxides. The zinc-aluminum layered material has a large specific surface area, is uniformly dispersed, is used for preparing a catalytic cracking hydrodesulfurization modification catalyst, and has good hydrodesulfurization and olefin reduction performances.
Description
Technical Field
The invention relates to a catalytic gasoline hydrodesulfurization modification catalyst and a preparation method thereof, which mainly prepares a zinc-aluminum layered material with uniform dispersion and high specific surface area by non-constant pH alternate titration of an aluminum-containing sodium carbonate solution and a zinc-containing solution, and the catalyst prepared by compounding the material and a molecular sieve material can be used for catalytic gasoline hydrodesulfurization and olefin reduction.
Background
The catalytic cracking gasoline in China has complicated sources and great property change. Particularly, compared with the foreign gasoline, the sulfur content is generally 500 v% at 100-. The selective hydrodesulfurization technology inevitably causes partial saturation of olefin to reduce the octane number when deep hydrodesulfurization is carried out, and the hydrodesulfurization modification catalyst prepared by compounding the hydrodesulfurization catalytic material and the molecular sieve can achieve hydrodesulfurization and convert the olefin into a high-octane number component to achieve the aim of desulfurization, olefin reduction and octane number maintenance.
The composite material of zinc oxide and aluminum oxide is often used as a desulfurization catalytic material in the field of hydrodesulfurization. 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 catalytic materials.
US5525210 discloses a process for the desulfurization of FCC gasoline, the major active component of which is an L acid, such as zinc oxide, supported on an alumina support, by impregnation and coprecipitation, wherein the impregnation process produces a material having a specific surface area of 142m 2/g after calcination at 815 ℃ and the coprecipitation process produces a material having a specific surface area of 74m 2/g after calcination at 704 ℃.
CN200710045746.4 discloses a catalytic cracking assistant capable of reducing the sulfur content of gasoline, which comprises a composite oxide of zinc aluminum spinel, uniformly dispersed zinc oxide and optionally at least one rare earth metal oxide, and is prepared by roasting a mixture of a zinc aluminum layered substance with a hydrotalcite-like structure and an optionally rare earth hydrated oxide, wherein the chemical formula of the mixture is ZnAl 2 O 4 (1-9) ZnO (0-0.5) RE 2 O 3, the preparation method is that sodium hydroxide and soluble inorganic sodium salt are dripped into a mixed solution of zinc salt, aluminum salt and rare earth ions, the pH value of the solution is 8-11, the solution is roasted at 500-1000 ℃ for 1-4h, the assistant is mixed with a conventional FCC catalyst and/or an activity enhancing assistant after being formed and applied to the catalytic cracking process, the assistant has the function of reducing the sulfur content of gasoline and has excellent hydrothermal stability, and the material needs to be roasted at a higher temperature and the specific surface area is 120m 2/g at most after being roasted to obtain the zinc aluminum spinel structure.
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 ℃, wherein the molar ratio of the raw materials is Zn to Al to water is 1: 2: 16-35, the mass of zinc oxide is 100%, the addition amount of the pore-expanding agent is 0.5-30%, the pore-expanding 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 60-300 m 2/g, the proportion of zinc and aluminum 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 oxide which is uniformly dispersed is not contained.
2CN201310625314.6 discloses a preparation method of a photocatalytic material with strong adsorption and high visible light degradation performance, which 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, wherein the material is used for adsorbing and degrading organic pollutants.
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 high-efficiency sulfur transfer agent for catalytic cracking flue gas, 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 600 ℃ 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 SO x adsorption and desorption performances and good mechanical strength.
CN200910087590.5 discloses a desulfurizing agent for reforming raw oil and a preparation method thereof, and the preparation method of the catalyst relates to a blending method, a eutectic method and a coprecipitation method, and is characterized in that the catalyst comprises, by weight, 10% -40% of ZnO, 15% -22% of NiO, 10% -17% of Al 2 O 3, 5% -22% of SiO 2, and the balance unavoidable impurities.
CN201310089762.9 discloses a nanometer size layered composite hydroxide and a fractional precipitation preparation method thereof, which adopts soluble salt of metal and alkali as raw materials, and makes metal ions forming an LDH laminate precipitate respectively through fractional precipitation reaction, and produces LDH in the second step of precipitation process, the specific surface area is 140-280m 2/g, compared with the coprecipitation method, the invention adopts twice precipitation, but the prepared LDH material has higher specific surface area, but the reaction time of the invention is longer, and the reaction time given in the embodiment is more than 10 hours.
A process for preparing Zn-Al spinel used for decreasing the sulfur content in catalytically cracked gasoline includes such steps as proportionally adding sodium metaaluminate solution and zinc nitrate solution to distilled water at 40 deg.C in the same speed in the ratio of m (Al 2 O 3)/m (ZnO) to 9, mixing, adding 16% sodium hydroxide solution, regulating pH value to 8.6, ageing the resultant deposit for 15min, adding small amount of sodium hydroxide solution, regulating pH value to 9.0, filtering and washing the deposit for 3 times to remove Na +, drying the deposit at 120 deg.C for 4 hr, and calcining at 700 deg.C for 2 hr.
Disclosure of Invention
The invention aims to provide a catalytic gasoline hydrodesulfurization modification catalyst, which is used for preparing a zinc-aluminum hydrotalcite-like structure layered material, namely a zinc-aluminum layered material, by alternately titrating non-constant pH of an aluminum-containing sodium carbonate solution and a zinc-containing solution, wherein the catalyst prepared by compounding the material with a molecular sieve material can be used for catalytic gasoline hydrodesulfurization modification.
The invention aims to solve the technical problem that a zinc-aluminum hydrotalcite-like structure layered material is prepared by alternately titrating an aluminum-containing sodium carbonate solution and a zinc-containing solution under the condition of non-constant pH value, and the material has a large specific surface area and zinc and aluminum are uniformly dispersed, so that the material can be used as a catalytic material and a molecular sieve material to be compounded and then used for preparing a catalytic cracking hydrodesulfurization modification catalyst. Solves the problems that the specific surface area of the zinc oxide-containing material prepared by the conventional preparation method is lower and the application of the zinc oxide-containing material as a catalytic material is limited.
The hydrodesulfurization modification catalyst is characterized in that the weight of the catalyst is 100%, the content of a molecular sieve is 5-70 wt%, the content of VIB group metals is 2-10 wt% calculated by oxides, the content of VIII group metals is 1-5 wt% calculated by oxides, the zinc-aluminum layered material prepared by non-constant pH alternate titration is 5-50%, and the content of phosphorus is 0-10 wt% calculated by oxides.
The zinc-aluminum layered material is used for a hydrodesulfurization modification catalyst, the zinc-aluminum layered material is added into a molecular sieve and kneaded to prepare a carrier, soluble salt containing VIB group metal, VIII group metal and phosphorus element is prepared into impregnation liquid, the carrier is impregnated to obtain a catalyst precursor containing the zinc-aluminum material, the catalyst precursor is dried at 80-150 ℃, and the catalyst precursor is roasted at 550 ℃ for 4-10 hours to obtain a catalyst finished product.
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 obtained 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 mixed solution; 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; alternately titrating the aluminum-containing solution and the zinc-containing solution according to the method until the zinc-containing solution is completely dripped into the mixed solution, dripping the aluminum-containing solution for the last time, 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 finish all titration processes within 0.5-6 h;
4) Aging at 75-95 deg.C for 2-8h, cooling and washing to neutrality, and drying at 80-140 deg.C in air atmosphere for 4-10h to obtain zinc-aluminum layered material.
The hydrodesulfurization modification catalyst comprises a zinc-aluminum layered material, wherein the zinc-aluminum layered material mainly comprises a zinc-aluminum layered material represented by the chemical formula Zn x Al y (OH) z (CO 3) m. nH 2 O, wherein x is a number from 0.55 to 0.75, y is a number from 0.13 to 0.7, z is a number from 1.55 to 2.50, m is a number from 0.15 to 0.20, n is a number from 1 to 10, the value of x/y is a number from 0.75 to 5.70, preferably x/y is a number from 0.93 to 2.50, more preferably x/y is a number from 1.15 to 1.90, the specific surface area is 150-280m 2/g, preferably 180-280m 2/g, more preferably 200-280m 2/g, when the molar ratio of zinc to aluminum is controlled within the range of 0.93-1.90, the specific surface area is 180-280 m/g, and the specific surface area is preferably 180-180 m 7390 when the molar ratio of zinc is controlled within the range of 493 2/g, and the range of 0.93-1.90.
the hydrodesulfurization modification catalyst can be ZSM-5 and/or SAPO-11, the molecular sieve content is 5-70 wt%, preferably 30-65 wt%, the tungsten and/or molybdenum content is 2-10 wt%, preferably 2-5 wt% calculated by oxide, and the nickel and/or cobalt content is 1-5 wt%, preferably 1-3 wt% calculated by oxide, based on the weight of the catalyst.
the soluble zinc salt can be one or more of zinc nitrate, zinc acetate and zinc chloride.
The zinc-aluminum layered material is used for a hydrodesulfurization modification catalyst, and the reaction process conditions are that the reaction temperature is 170-350 ℃, the reaction pressure is 1.5-2.4MPa, the volume space velocity is 1.5-4.0h -1, and the hydrogen-oil volume ratio is 150-500: 1.
Compared with the prior art, the zinc-aluminum layered material is prepared by non-constant pH alternate titration, namely, the aluminum-containing sodium carbonate solution and the 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 the multiple alternate titration among the aluminum and zinc solutions enables the pH value to swing between acid and alkali, which is beneficial to orderly accumulation of aluminum and zinc precursors into a layered structure, the obtained zinc-aluminum layered material is uniformly dispersed, the specific surface area can be regulated and controlled between 150 and 280m 2/g, the problem that the zinc-aluminum layered material obtained by one-step titration of the zinc-aluminum mixed solution by adopting the alkaline solution needs high-temperature roasting to fix zinc oxide is solved, and the hydrothermal treatment process is reduced.
Drawings
Fig. 1 is an XRD characterization chart of catalyst precursors a to F of the zinc-aluminum-containing layered materials prepared in examples 1 to 6, the XRD spectrum of samples 1 to 6 contains characteristic peaks of XRD of Zn x Al y (OH) z (CO 3) m. nH 2 O phase, which indicates that the catalyst precursors contain zinc-aluminum layered materials.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
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 method adopts Lanzhou petrochemical gasoline as a raw material, the sulfur content is 300mg/kg, the RON is 91.5, and the olefin is 40%.
Example 1
Dissolving 2.4kg of zinc nitrate in 12L of water to prepare a zinc-containing solution, dissolving 0.32kg of sodium metaaluminate and 0.40kg of sodium carbonate in 5L of water to prepare an aluminum-containing solution, equally dividing the zinc-containing solution into 4 parts, taking 3L of zinc-containing solution each 3L, controlling the temperature of a system to be 75 ℃, dropwise adding the aluminum-containing solution into the zinc-containing solution until the pH value reaches 9.4, stopping dropwise adding the aluminum-containing solution, dropwise adding the 3L of zinc-containing solution into a mixing system, continuously dropwise adding the aluminum-containing solution until the pH value reaches 9.4, alternatively titrating the aluminum-containing solution and the zinc-containing solution until the zinc-containing solution is completely added into the mixing system, finally dropwise adding the aluminum-containing solution until the pH value reaches 9.4, titrating for 2 hours in total to obtain a mixture, aging the mixture at 75 ℃ for 4 hours, cooling and washing to be neutral, and drying the mixture in an air atmosphere at 130 ℃ for 2 hours to obtain a zinc-aluminum layered material 1, wherein the molecular formula is Zn 0.60 Al 0.50 (OH) 2.33 (CO 3.
Taking 1kg of zinc-aluminum layered material 1 and 1kg of molecular sieve ZSM-5 to mix and extrude the mixture into a carrier; 0.135kg of ammonium molybdate, 0.072kg of cobalt nitrate and 0.039kg of ammonium dihydrogen phosphate are added into 0.2L of ammonia water, diluted by 0.6L of deionized water, and dipped into a carrier in equal volume to obtain a catalyst precursor A, and the catalyst precursor A is dried at 90 ℃ and then roasted at 550 ℃ for 4 hours to obtain the catalyst A. The composition is shown in Table 2.
Comparative example 1
Dissolving 2.4kg of zinc nitrate in 12L of water to prepare a zinc-containing solution, dissolving 0.32kg of sodium metaaluminate and 0.40kg of sodium carbonate in 5L of water to prepare an aluminum-containing solution, controlling the temperature of the system to be 75 ℃, dropwise adding the aluminum-containing solution into the zinc-containing solution until the pH value reaches 9.4, controlling the titration time to be 2 hours in total, aging the obtained mixture at 75 ℃ for 4 hours, cooling and washing to be neutral, and drying in an air atmosphere at 130 ℃ for 2 hours to obtain the zinc-aluminum mixture 1 with the zinc-aluminum molar ratio of 1.20 and the specific surface area of 145m 2/g.
Mixing 1kg of zinc-aluminum mixture 1 and 1kg of molecular sieve ZSM-5, extruding the mixture into a strip to form a carrier; 0.135kg of ammonium molybdate, 0.072kg of cobalt nitrate and 0.039kg of ammonium dihydrogen phosphate are added into 0.2L of ammonia water, diluted by 0.6L of deionized water, impregnated with a carrier in the same volume, dried at 90 ℃ and roasted at 550 ℃ for 4 hours to obtain the catalyst A1. The composition is shown in Table 2.
Compared with the comparative example 1, the zinc-aluminum layered material can be obtained by alternative titration of zinc and aluminum solutions in the example 1, and the specific surface area of the example 1 is higher under the condition that the molar ratio of zinc and aluminum of the two materials is the same.
Example 2
Dissolving 1.9kg of zinc chloride in 20L of water to prepare a zinc-containing solution, dissolving 0.40kg of sodium metaaluminate and 0.80kg of sodium carbonate in 8.5L of water to prepare an aluminum-containing solution, taking 8L of the zinc-containing solution, controlling the temperature of a system to be 65 ℃, dropwise adding the aluminum-containing solution into the zinc-containing solution until the pH value reaches 9.1, equally dividing the rest of the zinc-containing solution into 3 parts, alternately titrating 4L of the aluminum-containing solution and the zinc-containing solution in each part until the zinc-containing solution is completely added into a mixing system, finally dropwise adding the aluminum-containing solution until the pH value reaches 9.1, aging the obtained mixture for 6 hours at 76 ℃, cooling and washing the mixture to be neutral, and drying the mixture for 10 hours in an air atmosphere at 90 ℃ to obtain a zinc-aluminum layered material 2 with the molecular formula of Zn 0.67 Al 0.33 (OH) 2.03 (CO 3) 0.150.4H 2 O, the molar ratio of zinc to aluminum to.
Mixing 0.3kg of zinc-aluminum layered material 2, 0.3kg of molecular sieve ZSM-5 and 0.3kg of molecular sieve SAPO-11, extruding the mixture into a strip to form a carrier; dissolving 0.061kg of ammonium molybdate, 0.056kg of cobalt nitrate and 0.05kg of ammonium nitrate in 0.35L of deionized water, adding 0.4L of ammonia water, impregnating the carrier in an equal volume to obtain a catalyst precursor B, drying at 100 ℃, and roasting at 510 ℃ for 6 hours to obtain the catalyst B. The composition is shown in Table 2.
Comparative example 2
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, and drying and grinding a filter cake to obtain the zinc oxide material with the specific surface area of 60M 2/g.
Mixing 0.3kg of zinc oxide material, 0.3kg of molecular sieve ZSM-5 and 0.3kg of molecular sieve SAPO-11, extruding the mixture into a strip to form a carrier; 0.061kg of ammonium molybdate, 0.056kg of cobalt nitrate and 0.05kg of ammonium nitrate are dissolved in 0.35L of deionized water, 0.4L of ammonia water is added, the carrier is soaked in the ammonia water in the same volume, and the catalyst B1 is obtained by drying the carrier at 100 ℃ and then roasting the carrier for 6 hours at 510 ℃. The composition is shown in Table 2.
Comparative example 2 compared to example 2, the specific surface area of the zinc oxide material prepared by titrating a zinc-containing solution with sodium hydroxide was lower.
Example 3
Dissolving 800g of zinc nitrate in 4L of water to prepare a zinc-containing solution, dissolving 120g of sodium metaaluminate and 120g of sodium carbonate in 1.7L of water to prepare an aluminum-containing solution, taking 2L of the zinc-containing solution, controlling the temperature of a system to be 60 ℃, dropwise adding the 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 the zinc-containing solution into a mixing system, continuously dropwise adding the aluminum-containing solution until the pH value reaches 9, and titrating for 4 hours in total, aging the obtained mixture at 85 ℃ for 4 hours, cooling and washing the mixture to be neutral, and drying the mixture in an air atmosphere at 120 ℃ for 5 hours to obtain the zinc-aluminum layered material 3, wherein the molecular formula is Zn 0.59 Al 0.63 (OH) 2.44 (CO 3) 0.195.6H 2 O, the molar ratio of zinc to aluminum.
Mixing 50g of zinc-aluminum layered material 3, 125g of molecular sieve ZSM-5 and 25g of molecular sieve SAPO-11, extruding the mixture into strips to form a carrier; dissolving 21.6g of ammonium molybdate and 12.1g of cobalt nitrate in 75ml of ammonia water, impregnating a carrier in an equal volume to obtain a catalyst precursor C, drying at 100 ℃, and roasting at 480 ℃ for 9 hours to obtain the catalyst C. The composition is shown in Table 2.
Comparative example 3
Dissolving 800g of zinc nitrate and 550g of aluminum nitrate in 4L of water to prepare a zinc-containing and aluminum-containing solution, dissolving 120g of sodium carbonate in 1.7L of water to prepare a sodium carbonate solution, controlling the temperature of the system to be 60 ℃, dropwise adding the zinc-containing and aluminum-containing solution into the sodium carbonate solution until the pH value reaches 9, stopping dropwise adding the aluminum-containing solution, dropwise adding the remaining 2L of the zinc-containing solution into a mixing system, continuously dropwise adding the aluminum-containing solution until the pH value reaches 9, aging the obtained mixture at 85 ℃ for 4 hours, cooling and washing to be neutral, drying in 120 ℃ air atmosphere for 5 hours, and obtaining the coprecipitation product with the zinc-aluminum molar ratio of 0.94 and the specific surface area of 120m 2/g.
Mixing 50g of zinc-aluminum mixture material with 125g of molecular sieve ZSM-5 and 25g of molecular sieve SAPO-11, extruding the mixture into strips to form a carrier; dissolving 21.6g of ammonium molybdate and 12.1g of cobalt nitrate in 75ml of ammonia water, impregnating the carrier in an equal volume, drying at 100 ℃, and roasting at 480 ℃ for 9 hours to obtain the catalyst C1. The composition is shown in Table 2.
In comparison with comparative example 3, in example 3, sodium carbonate and aluminum nitrate are prepared into a mixed solution and are alternately titrated with a zinc-containing solution, and although the molar ratio of zinc to aluminum of the materials obtained by the two preparation methods is the same, the specific surface area of example 3 is higher.
Example 4
Dissolving 1.6kg of zinc nitrate in 8L of water to prepare a zinc-containing solution, dissolving 0.11kg of sodium metaaluminate and 0.38kg of sodium carbonate in 3.4L of water to prepare an aluminum-containing solution, equally dividing the zinc-containing solution into 4 parts, taking 2L of zinc-containing solution per part, controlling the temperature of a system to be 75 ℃, dropwise adding the aluminum-containing solution into the zinc-containing solution until the pH value reaches 8.7, stopping dropwise adding the aluminum-containing solution, dropwise adding the 2L of zinc-containing solution into a mixing system, continuously dropwise adding the aluminum-containing solution until the pH value reaches 8.7, alternately titrating the aluminum-containing solution and the zinc-containing solution until the zinc-containing solution is completely added into the mixing system, finally dropwise adding the aluminum-containing solution until the pH value reaches 8.7, titrating for 6 hours in total to obtain a mixture, aging the mixture at 90 ℃ for 6 hours, cooling and washing to be neutral, drying in an air atmosphere at 110 ℃ for 6 hours to obtain a zinc-aluminum layered material 4 with a molecular formula of Zn 0.74 Al 0.21 (OH) 1.72 (CO 3.56.3929.
Mixing 1.1kg of zinc-aluminum layered material 4 and 0.9kg of molecular sieve SAPO-11, extruding the mixture into strips to form a carrier; 0.216kg of ammonium molybdate and 0.346kg of nickel acetate are dissolved in 0.75L of ammonia water, the carrier is soaked in the ammonia water in the same volume to obtain a catalyst precursor D, and the catalyst precursor D is dried at 130 ℃ and then roasted at 460 ℃ for 10 hours to obtain the catalyst D. The composition is shown in Table 2.
Comparative example 4
Dissolving 1.6kg of zinc nitrate in 8L of water to prepare a zinc-containing solution, dissolving 0.11kg of sodium metaaluminate and 0.38kg of sodium carbonate in 3.4L of water to prepare an aluminum-containing solution, controlling the temperature of the system to be 75 ℃, dropwise adding the aluminum-containing solution into the zinc-containing solution until the pH value reaches 8.7, controlling the titration time to be 6 hours in total, aging the obtained mixture at 90 ℃ for 6 hours, cooling and washing to be neutral, drying in an air atmosphere at 110 ℃ for 6 hours, and obtaining a coprecipitation product with the zinc-aluminum molar ratio of 3.04 and the specific surface area of 124m 2/g.
Mixing 1.1kg of zinc-aluminum mixture material and 0.9kg of molecular sieve SAPO-11, extruding the mixture into strips to form a carrier; 0.216kg of ammonium molybdate and 0.346kg of nickel acetate are dissolved in 0.75L of ammonia water, the carrier is soaked in the ammonia water in the same volume, and then the catalyst D1 is obtained after drying at 130 ℃ and roasting at 460 ℃ for 10 h. The composition is shown in Table 2.
compared with the comparative example 4, the zinc-aluminum molar ratio and the specific surface area of the obtained zinc-aluminum layered material are higher in example 4 by adopting the alternative titration of the zinc and aluminum solutions.
Example 5
0.61 0.42 2.06 3 0.165 2 2296g of zinc acetate is dissolved in 2L of water to prepare a zinc-containing solution, 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 is equally divided into 3 parts, each part is 0.67L, 0.67L of zinc-containing solution is taken, the temperature of a system is controlled to be 55 ℃, aluminum-containing solution is dripped into the zinc-containing solution until the pH value reaches 9.3, the dropwise addition of aluminum-containing solution is stopped, 0.67L of aluminum-containing solution is continuously dripped into the mixing system until the pH value reaches 9.3, the dropwise addition of aluminum-containing solution is stopped, 0.67L of zinc-containing solution is dripped into the mixing system, the aluminum-containing solution is finally dripped into the mixing system until the pH value reaches 9.3, the titration time is 3H in total, the obtained mixture is aged for 7H at 80 ℃, cooled and washed to be neutral, and dried for 8H in an air atmosphere at 100 ℃, so that a zinc-aluminum layered material 5 is obtained, the molecular formula of Zn.
Mixing 75g of zinc-aluminum layered material 5 and 125kg of molecular sieve ZSM-5, extruding the mixture into a strip to form a carrier; 5.4g of ammonium molybdate and 38.4g of nickel acetate are dissolved in 80ml of deionized water, a carrier is impregnated in an equal volume to obtain a catalyst precursor E, and the catalyst precursor E is dried at 120 ℃ and then roasted at 550 ℃ for 4 hours to obtain the catalyst E. The composition is shown in Table 2.
Comparative example 5
125kg of molecular sieve ZSM-5 and 75g of pseudo-boehmite are mixed and extruded into a strip to form a carrier; 5.4g of ammonium molybdate and 38.4g of nickel acetate are dissolved in 80ml of deionized water, the carrier is soaked in the same volume, and then the catalyst E1 is obtained after drying at 120 ℃ and roasting at 550 ℃ for 4 h. The composition is shown in Table 2.
Example 6
Dissolving 4kg of zinc nitrate in 20L of water to prepare a zinc-containing solution, dissolving 0.34kg of sodium metaaluminate and 0.87kg of sodium carbonate in 8.5L of water to prepare an aluminum-containing solution, taking 10L of the zinc-containing solution, controlling the temperature of the system to be 40 ℃, dropwise adding the aluminum-containing solution into the zinc-containing solution until the pH value reaches 8.9, stopping dropwise adding the aluminum-containing solution, dropwise adding 5L of the zinc-containing solution into the mixing system, finally dropwise adding the aluminum-containing solution until the pH value reaches 8.9, and dropwise adding 5.5H in the mixing system, aging the obtained mixture at 76 ℃ for 8H, cooling and washing to be neutral, and drying the mixture at 120 ℃ in an air atmosphere for 4H to obtain the zinc-aluminum layered material 6 with the molecular formula of Zn 0.72 Al 0.29 (OH) 1.99 (CO 3) 0.145.6H 2 O, wherein the molar ratio of zinc to aluminum is 2.51, and the specific surface area is 199m 2/g.
Mixing 2kg of zinc-aluminum layered material 6, 1kg of molecular sieve ZSM-5 and 2kg of molecular sieve SAPO-11, extruding the mixture into a strip to form a carrier; dissolving 3.17kg of ammonium molybdate into a mixed solution of 5L of ammonia water and 15L of deionized water, respectively adding 2.43kg of cobalt nitrate, 0.96kg of ammonium dihydrogen phosphate and 2.5kg of ammonium nitrate to prepare impregnation liquid, impregnating a carrier in an equal volume to obtain a catalyst precursor F, drying at 140 ℃, and roasting at 500 ℃ for 7 hours to obtain the catalyst F. The composition is shown in Table 2.
Comparative example 6
Taking 5kg of zinc-aluminum layered material 6 and extruding into strips to form a carrier; dissolving 3.17kg of ammonium molybdate into a mixed solution of 5L of ammonia water and 15L of deionized water, respectively adding 2.43kg of cobalt nitrate, 0.96kg of ammonium dihydrogen phosphate and 2.5kg of ammonium nitrate to prepare impregnation liquid, impregnating a carrier in an equal volume, drying at 140 ℃, and roasting at 500 ℃ for 7 hours to obtain the catalyst F1. The composition is shown in Table 2.
catalysts A-F and contrast agents A1-F1 are respectively loaded into a 200ml adiabatic bed reactor, and after reduction is carried out for 4 hours at 450 ℃ by adopting hydrogen, the hydrodesulfurization modification is carried out on a gasoline raw material with the sulfur content of 300mg/kg, the olefin content of 40% and the RON of 91.5, and the reaction process conditions are as follows: the reaction pressure is 2.0MPa, and the volume ratio of hydrogen to oil is 250: 1. The evaluation results are shown in table 1:
TABLE 1
Table 2 catalyst compositions for examples 1-6 and comparative examples 1-6
| Catalyst and process for preparing same | A | A1 | B | B1 | C | C1 | D | D1 | E | E1 | F | F1 |
| ZSM-5 | 45.0 | 45.0 | 29.3 | 29.3 | 55.0 | 55.0 | - | - | 58.0 | 58.0 | 18.1 | - |
| SAPO-11 | - | - | 30.0 | 30.0 | 11.0 | 11.0 | 39.8 | 39.8 | - | - | 36.6 | - |
| Zinc-aluminium material | 46.0 | 46.0 | 33.4 | - | 23.0 | 23.0 | 48.0 | 48.0 | 35.0 | - | 36.0 | 90.7 |
| Zinc oxide | - | - | - | 33.4 | - | - | - | - | - | - | - | - |
| Alumina oxide | - | - | - | - | - | - | - | - | - | 35.0 | - | - |
| Molybdenum oxide | 5.0 | 5.0 | 4.5 | 4.5 | 8.0 | 8.0 | 8.0 | 8.0 | 2.0 | 2.0 | 4.7 | 4.7 |
| Cobalt oxide | 1.8 | 1.8 | 2.8 | 2.8 | 3.0 | 3.0 | - | - | - | - | 2.4 | 2.4 |
| Phosphorus oxide | 2.2 | 2.2 | - | - | - | - | - | - | - | - | 2.2 | 2.2 |
| Nickel oxide | - | - | - | - | - | - | 4.2 | 4.2 | 5.0 | 5.0 | - | - |
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (9)
- x y z 3 m 2 21. A hydrodesulfurization upgrading catalyst is characterized in that the catalyst comprises, based on 100% of the weight of the catalyst, 5-70 wt% of molecular sieve, 2-10 wt% of group VIB metal, 1-5 wt% of group VIII metal, based on oxide, 5-50 wt% of zinc-aluminum layered material prepared by non-constant pH alternate titration, 2.2-10 wt% of phosphorus, based on oxide, the zinc-aluminum layered material is prepared by the method comprising the steps of 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 obtained in 1) into 2-4 parts, taking an aluminum-containing solution in 2) at 40-80 ℃, dropping the aluminum-containing solution in 2) when the pH value reaches 8.5-9.5, stopping dropping the aluminum-containing solution when the pH value reaches 8.5-9.5, dropping the zinc-containing solution in the mixed solution, continuing to drop dropping the zinc-containing solution when the zinc-containing solution reaches 8.5-9.5, stopping dropping the aluminum-9.5, stopping dropping the dropping of the aluminum-containing solution when the pH value reaches 8.5, after the pH value reaches 8.5-9, after the final value, the final dropping of the above mentioned layered material, the above mentioned layered material is cooled by the above mentioned processes, the above mentioned processes are carried out 0-75 h, the above mentioned processes are carried out, the above mentioned processes are carried out the processes, the processes are carried out by the processes of 5-70.
- 2. The hydrodesulfurization upgrading catalyst of claim 1, wherein the group VIB metal is tungsten and/or molybdenum.
- 3. The hydrodesulfurization upgrading catalyst of claim 1, wherein the tungsten and/or molybdenum is present in an amount of 2 to 5 wt% on an oxide basis.
- 4. The hydrodesulfurization upgrading catalyst of claim 1, wherein the group VIII metal is nickel and/or cobalt, and the nickel and/or cobalt is present in an amount of 1-3 wt.% on an oxide basis.
- 5. The hydrodesulfurization upgrading catalyst of claim 1, wherein the molecular sieve is ZSM-5 and/or SAPO-11 and the molecular sieve content is 30-65 wt%.
- 6. The hydrodesulfurization upgrading catalyst of claim 1, wherein the zinc-aluminum layered material has a specific surface area of 200-280m 2/g.
- 7. The hydrodesulfurization upgrading catalyst of claim 1, wherein the zinc-aluminum molar ratio x/y of the zinc-aluminum layered material is a number from 1.15 to 1.90.
- 8. The hydrodesulfurization upgrading catalyst of claim 1 wherein the zinc/aluminum molar ratio x/y of the zinc/aluminum layered material is a number from 0.93 to 2.50 and the zinc/aluminum layered material has a specific surface area of 180-280m 2/g.
- 9. A method for preparing a hydrodesulfurization upgrading catalyst according to any one of claims 1 to 8, characterized in that the preparation process comprises: adding a zinc-aluminum layered material into a molecular sieve, kneading and molding to prepare a carrier, preparing soluble salt containing VIB group metal, VIII group metal and phosphorus into impregnation liquid, impregnating the carrier to obtain a catalyst precursor containing the zinc-aluminum material, drying at 80-150 ℃, and roasting at 550 ℃ for 4-10 hours to obtain a catalyst finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019201.7A CN106925337B (en) | 2015-12-29 | 2015-12-29 | Hydrodesulfurization modification catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019201.7A CN106925337B (en) | 2015-12-29 | 2015-12-29 | Hydrodesulfurization modification catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106925337A CN106925337A (en) | 2017-07-07 |
| CN106925337B true CN106925337B (en) | 2019-12-10 |
Family
ID=59442635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511019201.7A Active CN106925337B (en) | 2015-12-29 | 2015-12-29 | Hydrodesulfurization modification catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106925337B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148601A (en) * | 2007-09-10 | 2008-03-26 | 华东理工大学 | Catalytic cracking auxiliary agent for reducing sulfur content in gasoline and preparation method thereof |
| CN101294105A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Hydrogenation modification method of distillate oil |
| CN102407094A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Gasoline desulfurization adsorbent and preparation and application thereof |
| CN102515247A (en) * | 2011-12-09 | 2012-06-27 | 浙江工业大学 | Zinc-aluminum binary hydrotalcite and application thereof as photocatalytic material used for degrading methyl violet |
| CN104549475A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of FCC gasoline desulfurization agent composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721693B (en) * | 2012-10-10 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of Titanium oxide-aluminum oxide compound and its preparation method and application |
-
2015
- 2015-12-29 CN CN201511019201.7A patent/CN106925337B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101294105A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Hydrogenation modification method of distillate oil |
| CN101148601A (en) * | 2007-09-10 | 2008-03-26 | 华东理工大学 | Catalytic cracking auxiliary agent for reducing sulfur content in gasoline and preparation method thereof |
| CN102407094A (en) * | 2010-09-21 | 2012-04-11 | 中国石油天然气股份有限公司 | Gasoline desulfurization adsorbent and preparation and application thereof |
| CN102515247A (en) * | 2011-12-09 | 2012-06-27 | 浙江工业大学 | Zinc-aluminum binary hydrotalcite and application thereof as photocatalytic material used for degrading methyl violet |
| CN104549475A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of FCC gasoline desulfurization agent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106925337A (en) | 2017-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106867576A (en) | A kind of hydrodesulfurizationprocess process of gasoline | |
| CN106622204B (en) | A kind of zinc oxide material and preparation method containing gahnite | |
| CN102139217B (en) | Selective hydrogenation catalyst and preparation method thereof | |
| CN102319579B (en) | Hydrofining catalyst and preparation method thereof | |
| CN104549475A (en) | Preparation method of FCC gasoline desulfurization agent composition | |
| CN102319578A (en) | Hydrorefining catalyst and preparation method thereof | |
| TWI635170B (en) | Carrier for hydrogenation treatment catalyst, production method thereof, hydrogenation treatment catalyst, and production method thereof | |
| CN107511143B (en) | Regeneration method of adsorption desulfurizer | |
| CN106925338B (en) | Sulfur-carrying type hydrodesulfurization modification catalyst and preparation method thereof | |
| CN106925337B (en) | Hydrodesulfurization modification catalyst and preparation method thereof | |
| CN106622319B (en) | A kind of zinc-aluminium stratified material and preparation method | |
| CN110038584B (en) | Process for preparing hydrorefining catalyst | |
| CN107583660B (en) | Hydrodesulfurization catalyst containing zinc-aluminum layered material and preparation method thereof | |
| JP7395374B2 (en) | Hydrotreating catalyst for hydrocarbon oil, its production method, and hydrotreating method | |
| CN112742409B (en) | Catalyst for reducing mercaptan, preparation method and application thereof and method for reducing mercaptan in gasoline | |
| CN107583659B (en) | Catalyst for selective hydrodesulfurization and preparation method thereof | |
| CN106925249B (en) | Zinc oxide desulfurizer containing zinc-aluminum spinel | |
| CN107511128B (en) | Pretreatment method of adsorption desulfurizer | |
| CN102319572B (en) | Hydrotreatment catalyst and preparation method thereof | |
| CN106929091B (en) | A kind of catalytic gasoline hydrogenation desulfurization method for modifying | |
| CN108295826B (en) | Modified alumina dry glue powder and preparation method and application thereof | |
| JP4519379B2 (en) | Heavy hydrocarbon oil hydrotreating catalyst | |
| CN114471509B (en) | Alumina composition and method for preparing same | |
| CN113546671B (en) | Light gasoline cracking yield-increasing propylene catalyst containing ultra-macroporous silica gel, and preparation method and application thereof | |
| CN112717964B (en) | Paraffin hydrofining catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |