CN106955723B - A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents
A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil Download PDFInfo
- Publication number
- CN106955723B CN106955723B CN201610010255.5A CN201610010255A CN106955723B CN 106955723 B CN106955723 B CN 106955723B CN 201610010255 A CN201610010255 A CN 201610010255A CN 106955723 B CN106955723 B CN 106955723B
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- China
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- desulfurization
- hydrocarbon oil
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- sicn
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 142
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 127
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 127
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 127
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 124
- 230000023556 desulfurization Effects 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 110
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 66
- 239000011787 zinc oxide Substances 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000011230 binding agent Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 32
- 230000009467 reduction Effects 0.000 claims description 27
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 15
- 229910001593 boehmite Inorganic materials 0.000 claims description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- APIDIPGVBRXKEJ-UHFFFAOYSA-N acetic acid titanium Chemical compound [Ti].CC(O)=O.CC(O)=O APIDIPGVBRXKEJ-UHFFFAOYSA-N 0.000 claims description 2
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- CCLUHSUSTSVOPJ-UHFFFAOYSA-N propan-2-ol;tin Chemical compound [Sn].CC(C)O CCLUHSUSTSVOPJ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 21
- 150000004706 metal oxides Chemical class 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 94
- 239000003502 gasoline Substances 0.000 description 48
- 239000000203 mixture Substances 0.000 description 48
- 238000003756 stirring Methods 0.000 description 34
- 239000000126 substance Substances 0.000 description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- 230000032683 aging Effects 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 239000005864 Sulphur Substances 0.000 description 16
- 238000005336 cracking Methods 0.000 description 16
- 239000002283 diesel fuel Substances 0.000 description 16
- 238000001694 spray drying Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 238000005299 abrasion Methods 0.000 description 12
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- 239000003463 adsorbent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 210000002966 serum Anatomy 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 230000020477 pH reduction Effects 0.000 description 7
- 239000004110 Zinc silicate Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 6
- 235000019352 zinc silicate Nutrition 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000010451 perlite Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- ZHTHGKBAFPDEHL-UHFFFAOYSA-N silicic acid zinc Chemical compound [Zn].[Si](O)(O)(O)O ZHTHGKBAFPDEHL-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- -1 zinc oxide Chemical class 0.000 description 3
- 229940052228 zinc oxide paste Drugs 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- OWYGZENDPUIOCD-UHFFFAOYSA-N niobium(5+) oxygen(2-) tantalum(5+) Chemical compound [O-2].[Ta+5].[O-2].[Nb+5] OWYGZENDPUIOCD-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- HORCQSAKJDDBKB-UHFFFAOYSA-N 1-methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C=CC=C2C HORCQSAKJDDBKB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- 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
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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)
Abstract
本发明公开了一种烃油脱硫催化剂及其制备方法和烃油脱硫的方法。以该烃油脱硫催化剂的总重量为基准，该烃油脱硫催化剂含有：1)10～80重量％的至少一种选自IIB、VB和VIB族元素的金属氧化物；2)3～35重量％的耐热无机氧化物；3)5～40重量％的SiCN；4)5～30重量％的金属促进剂，所述金属促进剂选自钴、镍、铁和锰中的至少一种。该烃油脱硫催化剂具有更好的稳定性和更高的脱硫活性，更好的耐磨损性能，使用寿命更长。
The invention discloses a hydrocarbon oil desulfurization catalyst, a preparation method thereof, and a hydrocarbon oil desulfurization method. Based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10-80% by weight of at least one metal oxide selected from group IIB, VB and VIB elements; 2) 3-35% by weight % of heat-resistant inorganic oxide; 3) 5-40 wt % of SiCN; 4) 5-30 wt % of a metal promoter selected from at least one of cobalt, nickel, iron and manganese. The hydrocarbon oil desulfurization catalyst has better stability, higher desulfurization activity, better wear resistance and longer service life.
Description
Technical field
The present invention relates to the methods of a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil, and in particular, to
A kind of desulfurization of hydrocarbon oil catalyst, the desulfurization of hydrocarbon oil catalyst for preparing the method for desulfurization of hydrocarbon oil catalyst and being obtained by this method, with
And the method using desulfurization of hydrocarbon oil catalyst progress desulfurization of hydrocarbon oil.
Background technique
As people are to the pay attention to day by day of environmental protection, environmental regulation is also increasingly stringent, and reduces the sulphur of gasoline and diesel oil
Content is considered as improving one of the most important measure of air quality.Most of sulphur in China's gasoline products are from hot-working
Gasoline blending component, such as catalytically cracked gasoline.Therefore the reduction of sulfur content helps to reduce the production of China's gasoline in hot-working petroleum
The sulfur content of product.The existing gasoline products standard GB 17930-2011 " motor petrol " in China was required on December 31st, 2013,
Sulfur content must drop to 50 μ g/g in gasoline products.And following gasoline product quality standard will be more stringent.At this
In the case of kind, catalytically cracked gasoline, which has to pass through deep desulfuration just, can make gasoline products meet environmentally friendly requirement.
Currently, mainly selective catalytic desulfurhydrogenation and catalytic hydrogenation adsorb two kinds of desulfurization to the process for deep desulphurization of oil product
Method.Catalytic hydrogenation absorption desulfurization is to inhale the sulfide in hydrocarbon ils in certain temperature, pressure and realizing under conditions of face hydrogen
Attached removing, it is low and not high to the purity requirement of hydrogen which has the characteristics that hydrogen consumes, so that the technology is in terms of fuel desulfuration
It has broad application prospects.
CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, silica, oxidation al and ni, and wherein for nickel substantially to restore valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream contacted under the conditions of sulphur with the nickeliferous adsorbent composition.The composition is logical
It crosses and is granulated to form particle by the compound particles that zinc oxide, silica and aluminium oxide are formed, use nickel or nickeliferous chemical combination after dry, roasting
Object dipping, re-dry, roasting, reduction obtain.
CN1382071A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, silica, aluminium oxide and cobalt, and wherein for cobalt substantially to restore valence state presence, amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream contacted under the conditions of sulphur with the adsorbent composition containing cobalt.
US6150300 discloses a kind of method for preparing adsorbent, including prepares spheric granules: will (a) contain silica
Composition, the composition containing dispersion metal oxide in an aqueous medium and the composition containing zinc oxide mix shape
First mixture is not squeezed out at the first mixture and；(b) forming first mixture at spherical shape has diameter 10-
The particle of 1000mm.Wherein step (a) further includes mixing with metallic promoter agent.
CN1422177A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Object is made of zinc oxide, expanded perlite, aluminium oxide and promoter metals, wherein the promoter metals are substantially to restore
Valence state and contact under desulfurization conditions in Shi Nengcong cracking gasoline or diesel fuel stream remove sulphur amount exist.
CN1627988A discloses one kind suitable for the removing elementary sulfur from cracking gasoline and diesel fuel and vulcanization conjunction
The adsorbent composition of object, the adsorbent composition includes: zinc oxide, expanded perlite, aluminate and promoter metals,
Described in promoter metals will lead to when making cracking gasoline or diesel fuel stream and it is contacted under desulfurization conditions from cracking
The amount of desulfurization in the stream of gasoline or diesel fuel exists, and at least partly described promoter metals exist with 0 valence state.
CN1856359A discloses a kind of method for producing composition, comprising: a) mixing liquid, zinc compound, contain two
Silica material, aluminium oxide and co-catalyst, to form its mixture；B) dry mixture, to form dried mixing
Object；C) the dried mixture is calcined, to form the mixture through calcining；D) under suitable condition with reducing agent appropriate
By mixture reduction through calcining, to produce the composition and e) of the co-catalyst content in it with reduction valence state
Recycling changes composition.Co-catalyst contains selected from various metals such as nickel.
CN1871063A discloses a kind of method for producing composition, this method comprises: a) by liquid, zinc compound,
It is mixed containing earth silicon material, aluminium oxide to form its mixture；B) dry this of the mixture is mixed to form first
Through drying composite；C) described first is calcined through drying composite to form first through calcining mixt；D) by promotor knot
Close described first through within calcining mixt or on formed be promoted mixture；E) mixture and choosing are promoted described in making
It contacts from the acid of citric acid, tartaric acid and combinations thereof to be formed through contact mixture；F) by it is described through contact mixture it is dry with
Second is formed through drying composite；G) described second is calcined through drying composite to form second through calcining mixt；H) exist
Suitable reducing agent reduction described second is used wherein to promote containing reduction valence state through calcining mixt to produce under the conditions of appropriate
Into agent content composition and i) recycle the composition.
Although published adsorbent has certain desulfurization performance, with the raising of gasoline quality standard, to product
Content of sulfur in gasoline requires also constantly stringent.And such catalyst is easy to happen abrasion in use, needs to be continuously replenished
Catalyst improves operating cost.It can be seen that, it is desirable to provide it is a kind of to be urged with more high desulfurization activity and the novel of abrasion resistance properties
Agent.
Summary of the invention
The purpose of the invention is to overcome the desulphurizing activated low, structural instability of the adsorbent of the prior art and wear resistance
Can difference defect, provide the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil.
To achieve the goals above, the present invention provides a kind of desulfurization of hydrocarbon oil catalyst, with the total of the desulfurization of hydrocarbon oil catalyst
On the basis of weight, which contains: 1) at least one of 10~80 weight % is selected from IIB, VB and group vib element
Metal oxide；2) heat-resistant inorganic oxide of 3~35 weight %；3) SiCN of 5~40 weight %；4) 5~30 weight %
Metallic promoter agent, the metallic promoter agent is selected from least one of cobalt, nickel, iron and manganese.
The present invention also provides the methods for preparing desulfurization of hydrocarbon oil catalyst of the invention, comprising: (1a) is by SiCN, heat-resisting nothing
Machine adhesive oxides, water and acidic liquid contact to form slurries, and the slurries and at least one are selected from IIB, VB and VIB
The metal oxide of race's element is mixed to get carrier pulp；Or (1b) by heat-resistant inorganic oxide binder, water and Acidic Liquid
Body contacts to form slurries, and the slurries are mixed at least one metal oxide, SiCN selected from IIB, VB and group vib element
Obtain carrier pulp；(2) carrier pulp is formed, first dry, the first roasting, obtains carrier；(3) in the load
The precursor of metallic promoter agent is introduced in body, is then carried out second dry and the second roasting, is obtained catalyst precarsor；It (4) will be described
Catalyst precarsor restores in a hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst.
The present invention also provides desulfurization of hydrocarbon oil catalyst made from method of the invention.
The present invention also provides a kind of methods of desulfurization of hydrocarbon oil, comprising: in a hydrogen atmosphere, by hydrocarbon oil containing surphur and the present invention
The desulfurization of hydrocarbon oil catalyst of offer carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa.
Containing the stable SiCN of chemical property (carbonitride of silicium) in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, subtract
Lack the dependent interaction with metal oxides such as zinc oxide, avoids the formation such as silicic acid zinc material, such as the implementation that Fig. 1 is shown
The characteristic peak of zinc silicate is not present in XRD spectra after the hydrothermal aging for the desulfurization of hydrocarbon oil catalyst A1 that example 1 obtains.The present invention mentions
The desulfurization of hydrocarbon oil catalyst of confession has better stability and higher desulphurizing activated, can be more effective during desulfurization of hydrocarbon oil
Sulphur in hydrocarbon ils is adsorbed on desulfurization of hydrocarbon oil catalyst by ground, obtains the lower hydrocarbon ils of sulfur content.And hydrocarbon provided by the invention
Oily desulphurization catalyst has better abrasion resistance properties, and catalyst attrition is lower in sweetening process, and the service life is longer.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is XRD spectrum of the obtained desulfurization of hydrocarbon oil catalyst A1 of embodiment 1 before and after hydrothermal aging；
Fig. 2 is XRD spectrum of the obtained desulfurization of hydrocarbon oil catalyst B1 of comparative example 1 before and after hydrothermal aging.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, the hydrocarbon ils
Desulphurization catalyst contains: 1) at least one metal oxide selected from IIB, VB and group vib element of 10~80 weight %；2)3
The heat-resistant inorganic oxide of~35 weight %；3) SiCN of 5~40 weight %；4) metallic promoter agent of 5~30 weight %, it is described
Metallic promoter agent is selected from least one of cobalt, nickel, iron and manganese.
Preferably, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, the total weight with the desulfurization of hydrocarbon oil catalyst is
Benchmark, the desulfurization of hydrocarbon oil catalyst contain the metal oxide of 25~70 weight %, the heat resistant inorganic oxygen of 6~25 weight %
Compound, the SiCN of 10~30 weight %, the metallic promoter agent of 8~25 weight %.
It is highly preferred that on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, with the total weight of the desulfurization of hydrocarbon oil catalyst
On the basis of, which contains the metal oxide of 40~60 weight %, the heat resistant inorganic of 8~15 weight %
Oxide, the SiCN of 12~25 weight %, the metallic promoter agent of 12~20 weight %.
In the present invention, the content of each component in the desulfurization of hydrocarbon oil catalyst can be measured by XRD crystal phase analysis method.
According to the present invention, in the spectrogram that the desulfurization of hydrocarbon oil catalyst is obtained through XRD analysis 2 θ be 36.7 ° and 60.0 °
There are the crystal phase peaks of SiCN at place.
Contain the SiCN with hexagonal crystallographic texture in desulfurization of hydrocarbon oil catalyst provided by the invention as structural component, by
There is very high hydrothermal stability in structure SIC N, the catalyst can be effectively prevented from during carrying out desulfurization of hydrocarbon oil
Such as silicic acid zinc material is formed in composition, guarantees that the catalyst has better desulphurizing activated and stability.Preferably, the hydrocarbon ils is de-
Sulfur catalyst is not have the feature of zinc silicate at 22.0,25.54,48.9 and 59.4 in 2 θ in the XRD spectra after hydrothermal aging
Peak.The condition of the hydrothermal aging include: temperature be 500-700 DEG C, steam partial pressure 10-30kPa, the processing time be 10-
24h。
According to the present invention, at least one metal oxide selected from IIB, VB and group vib element can for zinc oxide,
At least one of cadmium oxide, vanadium oxide, niobium oxide tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide, it is described under preferable case
Metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide；It is highly preferred that the metal oxide is oxidation
Zinc.
In accordance with the present invention it is preferred that the metallic promoter agent is nickel and/or cobalt, the desulfurization of hydrocarbon oil catalyst can have
There is higher desulphurizing activated and regenerability；It can the metallic promoter agent be further preferably nickel.
In the case of, according to the invention it is preferred to, the heat-resistant inorganic oxide be aluminium oxide, titanium dioxide, zirconium dioxide and
At least one of stannic oxide.Preferably, the heat-resistant inorganic oxide is each component in the desulfurization of hydrocarbon oil catalyst
Between cementation is provided.Wherein, the aluminium oxide be gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide in extremely
Few one kind；Preferably, the aluminium oxide is gama-alumina.
The present invention also provides the methods for preparing desulfurization of hydrocarbon oil catalyst of the invention, comprising: (1a) is by SiCN, heat-resisting nothing
Machine adhesive oxides, water and acidic liquid contact to form slurries, and the slurries and at least one are selected from IIB, VB and VIB
The metal oxide of race's element is mixed to get carrier pulp；Or (1b) by heat-resistant inorganic oxide binder, water and Acidic Liquid
Body contacts to form slurries, and the slurries are mixed at least one metal oxide, SiCN selected from IIB, VB and group vib element
Obtain carrier pulp；(2) carrier pulp is formed, first dry, the first roasting, obtains carrier；(3) in the load
The precursor of metallic promoter agent is introduced in body, is then carried out second dry and the second roasting, is obtained catalyst precarsor；It (4) will be described
Catalyst precarsor restores in a hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst.
According to the present invention, the SiCN used selects specific structure that can provide desulfurization of hydrocarbon oil catalyst with preferably wear-resisting
Performance and desulphurizing activated.Under preferable case, SiCN has hexagonal crystallographic texture, in the form of sheets or column structure.Preferably, SiCN
Grain diameter is 1~20 μm, preferably 3~15 μm.Preferably, the specific surface area of SiCN is 1~30m2/g.Preferably, SiCN
N2 adsorption pore volume be 0.02~0.12cm3/g；It is further preferred that the N2 adsorption pore volume of SiCN is 0.03~0.10cm3/g。
In preparation method of the invention, being added for the metal oxide can be for the powder shape of the metal oxide
Formula is added, and is added in form of slurry again after water can also being added to be mixed into slurries the metal oxide.
In the present invention, at least one metal oxide selected from IIB, VB and group vib element can be zinc oxide, oxygen
At least one of cadmium, vanadium oxide, niobium oxide tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide；Preferably zinc oxide, oxidation
At least one of molybdenum and vanadium oxide；More preferably zinc oxide.
In the case of, according to the invention it is preferred to, it is viscous that heat-resistant inorganic oxide binder is selected from alumina binder, titanium dioxide
Tie at least one of agent, zirconium dioxide binder and stannic oxide binder.
Preferably, the alumina binder can be changed into for aluminium oxide or under conditions of the described first roasting
γ-Al2O3Substance.Under preferable case, the alumina binder can be selected from SB powder, hydrated alumina, Aluminum sol, a water
In softening aluminium stone (boehmite), false boehmite (boehmite), hibbsite and amorphous hydroted alumina extremely
Few one kind；Preferably, the alumina binder is at least one of SB powder, boehmite and Aluminum sol.
Preferably, the titanium dioxide binder is to hydrolyze in the acidic liquid, and in first roasting condition
Under be changed into the substance of anatase titanium dioxide.Further, the titanium dioxide binder can be selected from titanium tetrachloride, titanium
At least one of acetoacetic ester, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.
Preferably, the zirconium dioxide binder is to hydrolyze in the acidic liquid, and in first roasting condition
Under be changed into the substance of zirconium dioxide.Further, the zirconium dioxide binder can selected from zirconium chloride, zirconium oxychloride,
At least one of acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide.
Preferably, the stannic oxide binder is to hydrolyze in the acidic liquid, and in first roasting condition
Under be changed into the substance of stannic oxide.Further, the stannic oxide binder can be selected from tin tetrachloride, four isopropanols
At least one of tin, tin acetate, aqua oxidation tin and stannic oxide.
In the present invention, the titanium dioxide binder, zirconium dioxide binder and stannic oxide binder are molten with excess acid
Liquid contact, can hydrolyze and generate caking property colloidal solution.
According to the present invention, the acidic liquid can be acid or the aqueous solution of acid, and the acid can be selected from water-soluble
Inorganic acid and/or organic acid, the preferably described acid can be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the case of, according to the invention it is preferred to, the dosage of the acidic liquid makes the pH value 1~5 of the carrier pulp, excellent
It is selected as 1.5~4.
In the present invention, step (1a) and (1b) middle amount that water is added can be not specially limited, as long as can obtain described
Carrier pulp.Such as it is 5:1~10:1 that the amount of water and the weight ratio of the heat-resistant inorganic oxide binder, which is added,；Or
The weight ratio that the amount of water and the weight summation of the heat-resistant inorganic oxide binder and SiCN is added is 5:1~10:1.
In the present invention, the obtained carrier pulp can be the forms such as paste or slurries.It can be by the carrier pulp
Dry reshaping after thickening.The more preferable carrier pulp is slurry form, and it is 20-200 that granularity can be formed by spray drying
The microballoon of micron, reaches molding purpose.For the ease of spray drying, the solid content of the dry preceding carrier pulp can be 10
~50 weight %, preferably 20~50 weight %.It can also include that water is added during obtaining the carrier pulp, water
There is no particular limitation for additional amount, as long as obtained carrier pulp meets above-mentioned solid content.
In the present invention, the first drying means and condition in step (2) are known to those skilled in the art, such as dry
Method can be dry, dry, forced air drying.Under preferable case, the described first dry temperature can be room temperature~400
DEG C, preferably 100~350 DEG C；Described first dry time be 0.5h or more, preferably 0.5~100h, more preferably 2~
20h。
In the present invention, the first roasting condition in step (2) is also known to those skilled in the art, under preferable case,
The temperature of first roasting is 400~700 DEG C, preferably 450~650 DEG C；The time of first roasting is at least 0.5h,
Preferably 0.5~100h, more preferably 0.5~10h.
According to the present invention, for step (3) for metallic promoter agent to be added, the metallic promoter agent is as previously shown.The metal
The precursor of promotor is the substance that can be changed into the oxide of metallic promoter agent under the second roasting condition；Under preferable case,
The precursor of the metallic promoter agent can be selected from acetate, carbonate, nitrate, sulfate, the rhodanate of metallic promoter agent
At least one of with oxide.It is preferred that the precursor of the metallic promoter agent can be at least one of cobalt, nickel, iron and manganese
At least one of acetate, carbonate, nitrate, sulfate, rhodanate and oxide；The preferably vinegar of nickel and/or cobalt
At least one of hydrochlorate, carbonate, nitrate, sulfate, rhodanate and oxide；Can be preferably nickel nitrate and/or
Cobalt nitrate；More preferably at least one of the acetate of nickel, carbonate, nitrate, sulfate, rhodanate and oxide；
Particularly preferably nickel nitrate.
In the case of, according to the invention it is preferred to, the method that the precursor of metallic promoter agent is introduced on carrier is dipping or precipitating.
The dipping can be the solution or suspension impregnation carrier with the precursor of metallic promoter agent；The precipitating can be to promote metal
Solution or suspension into the precursor of agent are mixed with carrier, and ammonium hydroxide is then added by the precursor precipitation of metallic promoter agent in carrier
On.
In the case of, according to the invention it is preferred to, the described second dry temperature is 50~300 DEG C, preferably 100~250 DEG C；
Described second dry time was 0.5~8h, preferably 1~5h.
Preferably, the temperature of second roasting is 300~800 DEG C, preferably 450~750 DEG C；Second roasting
Time is 0.5h or more, preferably 1~3h.Second roasting can carry out in the presence of oxygen or oxygen-containing gas, until
Volatile materials is removed and the precursor of metallic promoter agent is converted into the oxide form of metallic promoter agent, obtains catalyst
Precursor.
According to the present invention, in step (4), the oxide of the metallic promoter agent in the catalyst precarsor is changed into metal
The catalyst precarsor can be restored under hydrogen atmosphere, deposit metallic promoter agent substantially with reduction-state by simple substance
Obtaining catalyst of the invention.The condition of the reduction is only by the oxide of the metallic promoter agent in the catalyst precarsor
It is changed into metal simple-substance, and the metal oxide in the carrier will not change.Under preferable case, the temperature of the reduction is
300~600 DEG C, preferably 400~500 DEG C；The time of the reduction is 0.5~6h, preferably 1~3h；The hydrogen gas
The content of hydrogen is 10~60 volume % in atmosphere.
In the present invention, step (4) can carry out catalyst precarsor reduction immediately after catalyst precarsor is made, can also be with
It is carried out (before being adsorbed for desulfurization) before use.Metal since metallic promoter agent is easy to oxidize, and in catalyst precarsor promotees
Exist in the form of an oxide into agent, therefore to be readily transported, catalyst precarsor is restored and carrying out desulfurization absorption by preferred steps (4)
Preceding progress.It is described to be reduced to make the metal in the oxide of metallic promoter agent substantially to exist with reduction-state, it obtains of the invention
Desulphurization catalyst.
In the case of, according to the invention it is preferred to, the heat-resistant inorganic oxide binder, SiCN, the metal oxide and
In the desulfurization of hydrocarbon oil catalyst that the additional amount of the precursor of the metallic promoter agent makes, with the desulfurization of hydrocarbon oil catalyst
On the basis of total weight, the desulfurization of hydrocarbon oil catalyst contains the metal oxide of 10~80 weight %, preferably comprise 25~
70 weight %, further preferably 40~60 weight %；Heat-resistant inorganic oxide containing 3~35 weight %, preferably comprises 6~25
Weight %, further preferably 8~15 weight %；SiCN containing 5~40 weight % preferably comprises 10~30 weight %, more excellent
Choosing contains 12~25 weight %；The metallic promoter agent containing 5~30 weight % preferably comprises 8~25 weight %, more preferably
Contain 12~20 weight %.
The present invention also provides desulfurization of hydrocarbon oil catalyst made from method of the invention.
The present invention also provides a kind of methods of desulfurization of hydrocarbon oil, this method comprises: in a hydrogen atmosphere, by hydrocarbon oil containing surphur with
Desulfurization of hydrocarbon oil catalyst provided by the invention carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa；Preferably, 400~
450 DEG C, carry out desulphurization reaction under 1.0~2.0MPa.The sulphur in hydrocarbon ils is adsorbed on catalyst in the process, to obtain
The hydrocarbon ils of low sulfur content.
In the present invention, the catalyst after reaction can be reused after regeneration.The regeneration carries out under oxygen atmosphere,
Regenerated condition includes: that regenerated pressure is normal pressure, and regenerated temperature is 400~700 DEG C, preferably 500~600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, it is also necessary to it is restored under hydrogen atmosphere,
The reducing condition of catalyst after regeneration includes: that temperature is 350~500 DEG C, preferably 400~450 DEG C；Pressure be 0.2~
2MPa, preferably 0.2~1.5MPa.
In the present invention, the hydrocarbon ils includes cracking gasoline and diesel fuel, wherein " cracking gasoline " means that boiling range is 40
It is from making biggish hydrocarbon molecule be cracked into heat or catalytic process compared with small molecule DEG C to 210 DEG C of hydrocarbon or its any fraction
Product.Applicable thermal cracking process includes but is not limited to coking, thermal cracking and visbreaking etc. and combinations thereof.Applicable catalysis
The example of cracking process includes but is not limited to fluid catalystic cracking and heavy oil catalytic cracking etc. and combinations thereof.Therefore, applicable
Catalytically cracked gasoline include but is not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and
Heavy oil cracked gasoline and combinations thereof.In some cases, in the methods of the invention be used as hydrocarbon-containifluids fluids when can before desulfurization incite somebody to action
The cracking gasoline fractionation and/or hydrotreating.The hydrocarbon that " diesel fuel " means that boiling range is 170 DEG C to 450 DEG C mixes
The liquid of object or its any fractional composition.Such hydrocarbon-containifluids fluids include but is not limited to light cycle oil, kerosene, straight-run diesel oil and add hydrogen
Handle diesel oil etc. and combinations thereof.
Term used herein " sulphur " represents any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or diesel engine combustion
The organosulfur compound being commonly present in material.Sulphur present in hydrocarbon-containifluids fluids of the present invention includes but is not limited to carbonyl sulfide (COS), two
Nitric sulfid (CS2), mercaptan or other thiophenes etc. and combinations thereof, especially include thiophene, benzothiophene, alkylthrophene,
The bigger thiophene-based chemical combination of the molecular weight being commonly present in alkyl benzothiophenes and methyldibenzothiophene and diesel fuel
Object.
Contain SiCN component in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, the component is in the multiple anti-of catalyst
Should with the effect of reacting with zinc oxide component is not easy in regenerative process, will not produce silicic acid zinc material make the desulfurization of hydrocarbon oil be catalyzed
Agent reduces desulphurizing activated because losing zinc oxide.Catalyst of the present invention has very high desulphurizing activated, while also having apparent
The property for increasing catalyst abrasion strength resistance is applicable to the reaction repeatedly of catalytically cracked gasoline or diesel fuel and regenerated
Sweetening process.
The present invention will be described in detail by way of examples below.
The desulfurization of hydrocarbon oil catalyst that embodiment and comparative example obtains uses X-ray diffractometer (Siemens company D5005 type)
XRD spectra is obtained, structure determination, Cu target, K α radiation, solid probe, tube voltage 40kV, tube current 40mA are carried out；
SiCN used in embodiment is SiCN-1, SiCN-2 and SiCN-3, by Sinopec catalyst Co., Ltd south
Capital branch company provides, and specific structural features are shown in Table 1,
Table 1
| Structure feature | SiCN-1 | SiCN-2 | SiCN-3 |
| Structure | Hexagonal, sheet | Hexagonal, column | Hexagonal, sheet |
| Average particle size *, μm | 9.5 | 3.6 | 15.0 |
| Specific surface area, m2/g | 10.0 | 26.0 | 3.2 |
| N2 adsorption pore volume, cm3/g | 0.08 | 0.10 | 0.03 |
* it is measured by laser particle analyzer (Mastersizer 2000 of Malvern company).
In the following Examples and Comparative Examples, the composition of desulfurization of hydrocarbon oil catalyst is calculated according to feeding intake.
Embodiment 1
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
(1) carrier is prepared.By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg and
The deionized water of 6.57kg mixes, and stirring obtained zinc oxide slurries after 30 minutes；
Take the SiCN-1 stirring of boehmite 1.81kg (catalyst Nanjing branch company contains butt 1.36kg) and 2.40kg
Then mixing is added deionized water 4.6kg and is uniformly mixed after slurries, to add the hydrochloric acid of the 30 weight % of 360ml (chemistry
Pure, Beijing Chemical Plant produces) make slurries pH=2.1,80 DEG C of aging 2h are warming up to after stirring acidification 1h, add zinc oxide slurries
1h is stirred after mixing obtains carrier pulp；
The carrier pulp is used into Niro Bowen Nozzle TowerTMThe spray dryer of model is done by spraying
Dry, spray drying pressure is 8.5 to 9.5MPa, and 500 DEG C of inlet temperature is hereinafter, outlet temperature is about 150 DEG C.By being spray-dried
The first 1h dry at 180 DEG C of the microballoon arrived, then roasts 1h at 635 DEG C and obtains carrier；
(2) catalyst precarsor processed.By the carrier of 3.2kg with the Nickelous nitrate hexahydrate of 3.51kg (Beijing chemical reagents corporation,
98.5 weight % of purity >) and 0.6kg deionized water solution dipping, obtained dipping object is after 180 DEG C of dry 4h, in sky
Catalyst precarsor is made in 635 DEG C of roasting 1h of gas atmosphere；
(3) it restores.By catalyst precarsor in hydrogen atmosphere reductase 12 h at 425 DEG C, obtain desulfurization of hydrocarbon oil catalyst A1.
The chemical composition of A1 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 24.0 weight %, alumina content
For 13.6 weight %, nickel content is 18.1 weight %.
Embodiment 2
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
By the SiCN-2 stirring of boehmite 1.56kg (catalyst Nanjing branch company contains butt 1.17kg) and 1.80kg
Then mixing is added deionized water 8.2kg and is uniformly mixed after slurries, to add the hydrochloric acid of the 30 weight % of 260ml and making slurries
80 DEG C of aging 2h are warming up to after pH=1.9, stirring acidification 1h.The Zinc oxide powder of 5.52kg is added after temperature reduction and is stirred
It mixes 1h and obtains carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A2.
The chemical composition of A2 are as follows: zinc oxide content is that 55.2 weight %, SiCN contents are 18.0 weight %, alumina content
For 11.7 weight %, nickel content is 15.1 weight %.
Embodiment 3
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The deionized water of the Zinc oxide powder of 4.93kg, the SiCN-3 of 2.1kg and 8.8kg is mixed, after stirring 30 minutes
Obtain zinc oxide and the mixed serum of SiCN；
Boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.36kg) and deionized water 4.6kg is taken to be uniformly mixed
After slurries, the hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) that the 30 weight % of 300ml are added makes slurries pH=2.5, stirring acid
80 DEG C of aging 2h are warming up to after changing 1h.Stirring 1h obtains carrier pulp after adding the mixed serum of zinc oxide and SiCN-3.
The spray drying forming of carrier pulp is carried out referring to the method for embodiment 1.
Catalyst precarsor and catalyst are prepared referring to the method for embodiment 1, unlike, it is molten with nickel nitrate and cobalt nitrate
Liquid substitutes Nickelous nitrate hexahydrate impregnated carrier, introduces active component nickel and cobalt, desulfurization of hydrocarbon oil catalyst A3 is obtained after reduction.
The chemical composition of A3 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 21.0 weight %, alumina content
For 13.5 weight %, nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Embodiment 4
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The deionized water of the Zinc oxide powder of 4.93kg, the SiCN-1 of 2.1kg and 8.8kg is mixed, after stirring 30 minutes
Obtain zinc oxide and the mixed serum of SiCN；
Boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.36kg) and deionized water 4.6kg is taken to be uniformly mixed
After slurries, the hydrochloric acid that the 30 weight % of 300ml are added makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h.
Stirring 1h obtains carrier pulp after adding the mixed serum of zinc oxide and SiCN.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A4.
The chemical composition of A4 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 21.0 weight %, alumina content
For 13.5 weight %, nickel content is 16.2 weight %.
Embodiment 5
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The titanium tetrachloride (Beijing Chemical Plant analyzes pure, 99 weight %) of 3.25kg is slowly added to the 5 weight % of 4.6kg
Dilute hydrochloric acid, be slowly stirred and crystalline titanium dioxide avoided to be precipitated, obtain the titanium colloidal sol pH=2.0 of pale yellow transparent；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 2.40kg SiCN-1 and
The deionized water of 6.57kg mixes, and stirring obtained zinc oxide and the mixed serum of SiCN after 30 minutes；Then it is molten that above-mentioned titanium is added
Glue stirs 1h and obtains carrier pulp after mixing；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A5.
The chemical composition of A5 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 24.0 weight %, and titanium dioxide contains
Amount is 13.6 weight %, and nickel content is 18.1 weight %.
Embodiment 6
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Titanium dioxide 1.25kg (Detitanium-ore-type, contain butt 1.17kg) is taken to be added to the deionized water and 1.0kg of 1.8kg
In the hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) of 30 weight %, pH=1.9 is stirred to react 1h, obtains the titanium of pale yellow transparent
Colloidal sol；
The deionized water of the Zinc oxide powder of SiCN-2,5.52kg of 1.80kg and 10.0kg are mixed under stiring,
Zinc oxide and the mixed serum of SiCN are obtained, above-mentioned titanium colloidal sol is then added and stirs 1h obtains carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A2.
The chemical composition of A2 are as follows: zinc oxide content is that 55.2 weight %, SiCN contents are 18.0 weight %, and titanium dioxide contains
Amount is 11.7 weight %, and nickel content is 15.1 weight %.
Embodiment 7
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Tetraethyl titanate 3.90kg (Aldrich analyzes pure, 99 weight %) and the deionized water of 1.6kg is taken to stir
In the case where be slowly added into 3.8kg 10 weight % nitric acid (analysis pure, Beijing Chemical Plant produce) solution in, pH=2.3,
And 1h is stirred, obtain the titanium colloidal sol of pale yellow transparent；
The deionized water of the Zinc oxide powder of 4.93kg, the SiCN-3 of 2.1kg and 8.8kg is mixed, after stirring 30 minutes
Zinc oxide and the mixed serum of SiCN are obtained, titanium colloidal sol is then added and stirs 1h and obtains carrier pulp；
The spray drying forming of carrier pulp is carried out referring to the method for embodiment 1.
Catalyst precarsor and catalyst are prepared referring to the method for embodiment 1, unlike, it is molten with nickel nitrate and cobalt nitrate
Liquid substitutes Nickelous nitrate hexahydrate impregnated carrier, introduces active component nickel and cobalt, desulfurization of hydrocarbon oil catalyst A7 is obtained after reduction.
The chemical composition of A7 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 21.0 weight %, and titanium dioxide contains
Amount is 13.5 weight %, and nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Embodiment 8
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Tetraethyl titanate 3.90kg (Aldrich analyzes pure, 99 weight %) and the deionized water of 1.6kg is taken to stir
In the case where be slowly added into 3.8kg 10 weight % nitric acid (analysis pure, Beijing Chemical Plant produce) solution in, pH=2.3,
And 1h is stirred, obtain the titanium colloidal sol of pale yellow transparent；
The deionized water of the Zinc oxide powder of 4.93kg, the SiCN-1 of 2.1kg and 8.8kg is mixed, after stirring 30 minutes
Obtain zinc oxide and the mixed serum of SiCN；Then titanium colloidal sol is added and stirs 1h and obtains carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A8.
The chemical composition of A8 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 21.0 weight %, and titanium dioxide contains
Amount is 13.5 weight %, and nickel content is 16.2 weight %.
Embodiment 9
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The zirconium chloride (Beijing Chemical Plant analyzes pure, 99 weight %) of 2.60kg is slowly added to the deionization of 5.0kg
Water, and the nitric acid solution of the 5 weight % of 4.6kg is added, it is slowly stirred and zirconium oxide crystallization is avoided to be precipitated, obtain pale yellow transparent
Zirconium colloidal sol pH=2.1；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 2.40kg SiCN-2 and
The deionized water of 6.57kg mixes, and stirring obtained zinc oxide and the mixed serum of SiCN after 30 minutes；Then it is molten that above-mentioned zirconium is added
Glue stirs 1h and obtains carrier pulp after mixing；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A9.
The chemical composition of A9 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 24.0 weight %, and zirconium dioxide contains
Amount is 13.6 weight %, and nickel content is 18.1 weight %.
Embodiment 10
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
By the tin tetrachloride (SnCl of 3.21kg4·5H2O, Alfa company, 99%) it is slowly added to the deionized water of 4.6kg,
And the nitric acid solution of the 5 weight % of 4.6kg is added, it is slowly stirred and oxidation tin crystals is avoided to be precipitated, it is molten to obtain colorless and transparent tin
Glue pH=2.1；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 2.40kg SiCN-3 and
The deionized water of 6.57kg mixes, and stirring obtained zinc oxide and the mixed serum of SiCN after 30 minutes；Then it is molten that above-mentioned tin is added
Glue stirs 1h and obtains carrier pulp after mixing；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A10.
The chemical composition of A10 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 24.0 weight %, stannic oxide
Content is 13.6 weight %, and nickel content is 18.1 weight %.
Comparative example 1
The deionized water of the Zinc oxide powder of 4.43kg and 6.57kg are mixed, stirring obtained zinc oxide paste after 30 minutes
Liquid；
Take the expanded perlite of boehmite 1.81kg (catalyst Nanjing branch company contains butt 1.36kg) and 2.46kg
(catalyst Nanjing branch company contains butt 2.40kg) is stirred, and deionized water 4.6kg is then added and is uniformly mixed, adds
The hydrochloric acid of the 30 weight % of 360ml makes slurries pH=2.1, is warming up to 80 DEG C of aging 2h after stirring acidification 1h, adds zinc oxide
Stirring 1h obtains carrier pulp after slurries mixing.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst B1.
The chemical composition of B1 are as follows: zinc oxide content is 44.3 weight %, and expanded perlite content is 24.0 weight %, oxidation
Aluminium content is 13.6 weight %, and nickel content is 18.1 weight %.
Comparative example 2
Boehmite 1.56kg (Shandong Aluminum Plant produces, and contains butt 1.17kg) and the diatomite of 1.85kg is taken (to contain butt
It 1.80kg) is stirred, deionized water 8.2kg is then added and is uniformly mixed, the hydrochloric acid for adding the 30 weight % of 260ml makes to starch
80 DEG C of aging 2h are warming up to after liquid pH=1.9, stirring acidification 1h.The Zinc oxide powder of 5.52kg is added simultaneously after temperature reduction
Stirring 1h obtains carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst B2.
The chemical composition of B2 are as follows: zinc oxide content is 55.2 weight %, and diatomite content is 18.0 weight %, and aluminium oxide contains
Amount is 11.7 weight %, and nickel content is 15.1 weight %.
Comparative example 3
The deionized water of the Zinc oxide powder of 4.93kg and 5.57kg are mixed, stirring obtained zinc oxide paste after 30 minutes
Liquid；
Take boehmite 1.80kg's (Shandong Aluminum Plant produces, and contains butt 1.35kg) and 2.16kg to go to the diatomite (world
Mining company contains butt 2.10kg) it is stirred, deionized water 4.6kg is then added and is uniformly mixed, adds the 30 of 300ml
The hydrochloric acid of weight % makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h.After adding the mixing of zinc oxide slurries
Stirring 1h obtains carrier pulp.
Method referring to embodiment 3 carries out the spray drying forming of carrier pulp and introduces active component nickel and cobalt, restores
After obtain desulfurization of hydrocarbon oil catalyst B3.
The chemical composition of B3 are as follows: zinc oxide content is 49.3 weight %, and diatomite content is 21.0 weight %, and aluminium oxide contains
Amount is 13.5 weight %, and nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Comparative example 4
The deionized water of the Zinc oxide powder of 4.93kg and 5.57kg are mixed, stirring obtained zinc oxide paste after 30 minutes
Liquid；
Taking boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.35kg) and the kaolin of 2.84kg, (Suzhou is high
Ling Tu factory contains butt 2.10kg) it is stirred, deionized water 3.6kg is then added and is uniformly mixed, adds 30 weights of 300ml
The hydrochloric acid of amount % makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h.It is stirred after adding the mixing of zinc oxide slurries
It mixes 1h and obtains carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of mixing taste and introduces active component nickel, obtains after reduction
Desulfurization of hydrocarbon oil catalyst B4.
The chemical composition of B4 are as follows: zinc oxide content is 49.3 weight %, and kaolin content is 21.0 weight %, and aluminium oxide contains
Amount is 13.5 weight %, and nickel content is 16.2 weight %.
Comparative example 5
According to the method for embodiment 1, it unlike, is prepared according to embodiment 2 in CN101774593A ordered porous
Carbonitride of silicium material obtains desulfurization of hydrocarbon oil with the SiCN-1 of the ordered porous carbonitride of silicium material substitution 2.40kg of 2.40kg
Catalyst B5.
The chemical composition of B5 are as follows: zinc oxide content is 44.3 weight %, and ordered porous carbonitride of silicium material content is 24.0
Weight %, alumina content are 13.6 weight %, and nickel content is 18.1 weight %.
Embodiment 11
(1) abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulfurization of hydrocarbon oil catalyst A1-A10 and B1-B5.It adopts
Method is worn with straight tube, method the results are shown in Table 2 with reference to RIPP 29-90 in " petrochemical analysis method (RIPP) experimental method ".
It is smaller to test obtained numerical value, shows that abrasion strength resistance is higher.It is when wearing under certain condition that abrasion index is corresponding in table 2
The percentage that fine powder generates.
(2) desulfurization performance is evaluated.To desulfurization of hydrocarbon oil catalyst A1-A10 and B1-B5 using the micro- anti-experimental provision of fixed bed into
Row HDS evaluation experiment, by 16 grams of desulfurization of hydrocarbon oil Catalyst packing in the fixed bed reactors that internal diameter is 30mm, a length of 1m.
Raw material hydrocarbon ils is the catalytically cracked gasoline of sulphur concentration 780ppm, reaction pressure 1.38MPa, hydrogen flowing quantity 6.3L/h, gasoline
Flow is 80mL/h, and reaction temperature is 410 DEG C, and the weight space velocity of raw material hydrocarbon ils is 4h-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur.
It is measured with sulfur content in product gasoline desulphurizing activated.Sulfur content is prompt using peace by offline chromatogram analysis method in product gasoline
The GC6890-SCD instrument of logical sequence company is measured.In order to which accurate characterization goes out desulfurization of hydrocarbon oil catalyst in industrial actual motion
Activity, the catalyst after the completion of HDS evaluation experiment carry out regeneration treatment under 550 DEG C of air atmosphere.Desulfurization of hydrocarbon oil is catalyzed
Agent carries out HDS evaluation experiment, its activity settles out substantially after regenerating 6 circulations, after the 6th stable circulation of catalyst
Sulfur content in product gasoline indicates the activity of catalyst, and sulfur content is as shown in table 2 in product gasoline after stablizing.
GB/T 503-1995 and GB/T 5487-1995 is respectively adopted to measure before reaction and gasoline after the 6th stable circulation
Motor octane number (MON) and research octane number (RON) (RON), the results are shown in Table 2.
Table 2
Note: the data in table in relation to octane number are the variable quantities of the octane number compared to feed gasoline."-" indicate compared to
The octane number of feed gasoline reduces.
1, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2, △ MON indicates the value added of product MON；
3, △ RON indicates the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
It can be seen that in desulfurization of hydrocarbon oil catalyst provided by the invention from the result data of table 2 containing SiCN component, hydrocarbon ils
The sulfur content for reducing gasoline still can be well realized after carrying out multiple circulation desulfurization in desulphurization catalyst, illustrates that the catalyst has
There is better desulphurizing activated and activity stability.And the abrasion index of the desulfurization of hydrocarbon oil catalyst is lower, illustrates to have more preferable
Abrasion strength resistance, so as to so that the desulfurization of hydrocarbon oil catalyst has longer service life.Desulfurization of hydrocarbon oil in comparative example 5 is urged
Agent contains ordered porous carbonitride of silicium material, the SiCN without containing the application, therefore abrasion index and is made much higher than embodiment
Catalyst abrasion index, illustrate that desulfurization of hydrocarbon oil catalyst provided by the invention can have better wear-resisting property.
Embodiment 12
Aging, condition are carried out to desulfurization of hydrocarbon oil catalyst A1-A10 and B1-B5 are as follows: catalyst is placed in 600 DEG C, water steaming
16h is handled under the atmosphere that gas partial pressure is 20kPa.
To before and after aging A1 and B1 carry out XRD spectra analysis, wherein XRD spectra such as Fig. 1 institute before and after A1 hydrothermal aging
Show, fresh dose there are the crystal phase peaks of SiCN at 2 θ=36.7 ° and 60.0 ° with aging agent；XRD spectrum before and after B1 hydrothermal aging
Figure is as shown in Figure 2.Do not occur in Fig. 1, in the XRD spectra after A1 hydrothermal aging zinc silicate 2 θ=22.0,25.54,
48.9 and 59.4 characteristic peak；In Fig. 2, occurs the features described above peak of zinc silicate in the XRD spectra after B1 hydrothermal aging.It adopts
With the silicic acid Zn content in the XRD spectra of crystal content quantitative analysis B1-B5, it the results are shown in Table 3.
The desulfurization performance that A1-A10 and B1-B5 after aging are evaluated with evaluation method identical with embodiment 11, is as a result shown in
Table 3.
Table 3
Note: the data in table in relation to octane number are the variable quantities of the octane number compared to feed gasoline."-" indicate compared to
The octane number of feed gasoline reduces.
1, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2, △ MON indicates the value added of product MON；
3, △ RON indicates the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
From the results shown in Table 3, it after ageing process, is not generated in the desulfurization of hydrocarbon oil catalyst that embodiment obtains
Zinc silicate, and the catalyst in comparative example 1-4, zinc oxide can generate zinc silicate with the material of silicon oxide-containing, to make catalyst
Desulphurizing activated reduction.
The data of product gasoline can also be seen that the still available high product of method provided by the invention from table 2 and 3
Yield of gasoline, the octane number of gasoline also change less.
Claims (14)
1. a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, which contains
Have:
1) zinc oxide of 10~80 weight %；
2) heat-resistant inorganic oxide of 3~35 weight %；
3) SiCN of 5~40 weight %；
4) metallic promoter agent of 5~30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；
Wherein, the heat-resistant inorganic oxide is at least one of aluminium oxide, titanium dioxide, zirconium dioxide and stannic oxide；
The SiCN has hexagonal crystallographic texture, in the form of sheets or column structure；The grain diameter of the SiCN is 1~20 μm；
The specific surface area of SiCN is 1 m2The m of/g~302/g；The N2 adsorption pore volume of SiCN is 0.02 cm3The cm of/g~0.123/g。
2. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein using the total weight of the desulfurization of hydrocarbon oil catalyst as base
Standard, the desulfurization of hydrocarbon oil catalyst contain the zinc oxide of 40~60 weight %, the heat-resistant inorganic oxide of 8~15 weight %, and 12
The SiCN of~25 weight %, the metallic promoter agent of 12~20 weight %.
3. desulfurization of hydrocarbon oil catalyst according to claim 1 or 2, wherein the desulfurization of hydrocarbon oil catalyst is obtained through XRD analysis
To spectrogram in 2 θ be 36.7 ° and 60.0 ° at there are the crystal phase peaks of SiCN.
4. the method for preparing desulfurization of hydrocarbon oil catalyst described in any one of claim 1-3, comprising:
SiCN, heat-resistant inorganic oxide binder, water and acidic liquid are contacted and to form slurries by (1a), by the slurries and oxygen
Change zinc and is mixed to get carrier pulp；
Or
(1b) contacts heat-resistant inorganic oxide binder, water and acidic liquid to form slurries, by the slurries and zinc oxide,
SiCN is mixed to get carrier pulp；
(2) carrier pulp is formed, first dry, the first roasting, obtains carrier；
(3) precursor of metallic promoter agent is introduced in the carrier, is then carried out second dry and the second roasting, is obtained catalyst
Precursor；
(4) catalyst precarsor is restored in a hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst；
Wherein, the heat-resistant inorganic oxide is at least one of aluminium oxide, titanium dioxide, zirconium dioxide and stannic oxide.
5. SiCN has hexagonal crystallographic texture according to the method described in claim 4, wherein, in the form of sheets or column structure.
6. method according to claim 4 or 5, wherein the grain diameter of SiCN is 1~20 μm；The specific surface area of SiCN
For 1 m2The m of/g~302/g；The N2 adsorption pore volume of SiCN is 0.02 cm3The cm of/g~0.123/g。
7. according to the method described in claim 6, wherein, the grain diameter of SiCN is 3~15 μm；The N2 adsorption pore volume of SiCN
For 0.03 cm3/ g~0.10cm3/g。
8. according to the method described in claim 4, wherein, the heat-resistant inorganic oxide binder be selected from alumina binder,
At least one of titanium dioxide binder, zirconium dioxide binder and stannic oxide binder；The alumina binder is
Selected from least one of hydrated alumina, Aluminum sol and amorphous hydroted alumina；The titanium dioxide binder is selected from tetrachloro
Change at least one of titanium, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide；It is described
Zirconium dioxide binder in zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide extremely
Few one kind；The stannic oxide binder is selected from tin tetrachloride, four isopropanol tin, tin acetate, aqua oxidation tin and stannic oxide
At least one of.
9. according to the method described in claim 8, wherein, the hydrated alumina is selected from boehmite, false boehmite
At least one of with hibbsite.
10. according to the method described in claim 4, wherein, the precursor of the metallic promoter agent is selected from the acetic acid of metallic promoter agent
At least one of salt, carbonate, nitrate, sulfate, rhodanate and oxide.
11. according to the method described in claim 4, wherein, the dosage of the acidic liquid makes the pH value 1 of the carrier pulp
~5；The acidic liquid is the aqueous solution of acid or acid, and the acid is selected from water-soluble inorganic acid and/or organic acid.
12. according to the method described in claim 4, wherein, the described first dry temperature is room temperature~400 DEG C, described first
The dry time is 0.5~8 h；The temperature of first roasting is 400~700 DEG C, and the time of first roasting is 0.5 h
More than；Described second dry temperature is 50~300 DEG C, and the described second dry time was 0.5~8 h；Second roasting
Temperature be 300~800 DEG C, it is described second roasting time be 0.5~4 h；The temperature of the reduction is 300~600 DEG C, institute
The time for stating reduction is 0.5~6h, and hydrogen content is 10~60 volume % in the hydrogen atmosphere.
13. desulfurization of hydrocarbon oil catalyst made from method described in any one of claim 4-12.
14. a kind of method of desulfurization of hydrocarbon oil, comprising: in a hydrogen atmosphere, will be any in hydrocarbon oil containing surphur and claim 1-4 and 13
Desulfurization of hydrocarbon oil catalyst described in one carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa.
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Citations (6)
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| CN1627988A (en) * | 2002-04-11 | 2005-06-15 | 科诺科菲利浦公司 | Desulfurization and sorbents for same |
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| CN104877556A (en) * | 2015-06-05 | 2015-09-02 | 贵阳明通炉料有限公司 | Composite coating with wear resistance, heat resistance and corrosion resistance |
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| CN1627988A (en) * | 2002-04-11 | 2005-06-15 | 科诺科菲利浦公司 | Desulfurization and sorbents for same |
| CN1871063A (en) * | 2003-08-25 | 2006-11-29 | 科诺科菲利浦公司 | Desulfurization and novel methods for same |
| CN102688783A (en) * | 2011-03-25 | 2012-09-26 | 中国石油化工股份有限公司 | Alkyne selective hydrogenation catalyst carrier and preparation method and catalyst thereof |
| CN103724034A (en) * | 2013-07-23 | 2014-04-16 | 太仓派欧技术咨询服务有限公司 | Silicon carbide whisker reinforced silicon nitride ceramic composite material and preparation method thereof |
| CN104294203A (en) * | 2014-09-11 | 2015-01-21 | 芜湖鼎瀚再制造技术有限公司 | Al2O3-TiO2 nano coating and preparation method thereof |
| CN104877556A (en) * | 2015-06-05 | 2015-09-02 | 贵阳明通炉料有限公司 | Composite coating with wear resistance, heat resistance and corrosion resistance |
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