CN109207192A - The desulfurizing method by adsorption of catalytically cracked gasoline - Google Patents
The desulfurizing method by adsorption of catalytically cracked gasoline Download PDFInfo
- Publication number
- CN109207192A CN109207192A CN201811347239.0A CN201811347239A CN109207192A CN 109207192 A CN109207192 A CN 109207192A CN 201811347239 A CN201811347239 A CN 201811347239A CN 109207192 A CN109207192 A CN 109207192A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- adsorption
- oxide
- zinc
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 72
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 29
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000023556 desulfurization Effects 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 24
- 239000011593 sulfur Substances 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 23
- 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 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 33
- 239000002253 acid Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- 150000002815 nickel Chemical class 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 150000003751 zinc Chemical class 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 9
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 9
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- WUCBICXOWNTEAT-UHFFFAOYSA-N [O--].[O--].[Ni++].[Zn++] Chemical compound [O--].[O--].[Ni++].[Zn++] WUCBICXOWNTEAT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims 4
- 229910052684 Cerium Inorganic materials 0.000 claims 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 3
- 229910052726 zirconium Inorganic materials 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 28
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008929 regeneration Effects 0.000 abstract description 13
- 238000011069 regeneration method Methods 0.000 abstract description 13
- -1 by weight percentage Substances 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 14
- 230000009467 reduction Effects 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 9
- 230000001172 regenerating effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004110 Zinc silicate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 5
- 235000019352 zinc silicate Nutrition 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003483 aging Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- GTEJAEKKYCZWHX-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[Al+3].[Zr+4].[Ce+3] Chemical compound [O--].[O--].[O--].[O--].[O--].[Al+3].[Zr+4].[Ce+3] GTEJAEKKYCZWHX-UHFFFAOYSA-N 0.000 description 1
- NPVCRCHUNAWBRA-UHFFFAOYSA-N [O-2].[Zn+2].[Ni]=O Chemical compound [O-2].[Zn+2].[Ni]=O NPVCRCHUNAWBRA-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of desulfurizing method by adsorption of catalytically cracked gasoline, using fixed bed reactors, gasoline is contacted with absorbing desulfurization catalyst, by weight percentage, catalyst includes: the zinc oxide of 25.0-50.0wt%, the nickel oxide of 0.5-25.0wt%, 2.0-55.0wt%ZSM-5 molecular sieve, the macroporous aluminium oxide of 20.0-50.0wt%, the cerium zirconium sosoloid of 1.0-25.0wt%；Reaction process condition are as follows: 280-400 DEG C of reaction temperature, reaction pressure 0.4-2.5MPa, volume space velocity 3-8h‑1, hydrogen to oil volume ratio 1-50.Catalyst working sulfur capacity is high, and loss of octane number is small, and regeneration and Reductive stability are good.
Description
Technical field
The present invention relates to a kind of desulfurizing method by adsorption of catalytically cracked gasoline.
Background technique
Gasoline absorbing desulfurization technology has become the important means of oil quality upgrading, which has high-sulfur selectivity,
Loss of octane number is small, investment and the lower feature of operating cost.Existing adsorbent is using silicon/aluminum material as carrier, oxygen mostly
Change the desulfuration adsorbent that zinc/active metal (such as nickel) is active component preparation, during the reaction due to carbon deposit and zinc sulphide,
The formation of zinc silicate, zinc aluminate causes the reduction of adsorption activity, and regeneration reducing is needed to restore the activity of adsorbent.Due to alkene
The generation of saturated reaction causes loss of octane number big.
Existing gasolene desulfurizing method by adsorption mainly comprises the steps that (1) desulfurization process: by sulfur-bearing hydrocarbon and hydrogen donor with
Adsorbent is mixed, and is obtained the sulfur-bearing hydrocarbon of desulfurization and is carried the spent agent of sulphur；(2) regeneration treatment: by the spent agent for carrying sulphur
It is mixed with oxygen-containing regeneration gas, obtains regenerative agent；(3) reduction treatment: the regenerative agent is mixed with reducing gas, is obtained
To the reducing/regenerating agent used as sorbent circulation；And it flows back reducing/regenerating agent obtained in step (3) as adsorbent
Sorbent circulation flow path is formed to step (1).With the continuous circulating reduction of adsorbent, regeneration, adsorbent often will appear brokenly
The problem of broken (strength reduction) and activity decline, and then lead to the decline of desulfuration efficiency.
CN103657709A discloses a kind of reaction absorption desulfurization-aromatization technique and its catalyst.The catalyst exists
When hydrorefining catalyst cracking gasoline feedstock not only have reaction absorption desulfurizing function, but also can coupling reaction absorption desulfurization it is anti-
Should and aromatization so that the technique and its catalyst developed can reach when modifying to raw material catalytic cracking gasoline
The octane number of product does not occur significantly to reduce while deep desulfuration.Using the FCC gasoline of sulfur content 300-800ppm as raw material,
Reach product gasoline S content<10ppm, olefin(e) centent reduces by 10 percentage points, and RON loses<1, yield of gasoline>95%.
CN101905161A is related to a kind of catalytic gasoline absorbing desulfurization catalyst and its preparation and application；Weight percent composition are as follows:
Activated zinc oxide 10-85%, white carbon black 5-80%, aluminium oxide 5-30%, oxygen nickel 4-45%；(1) by titanium tetrachloride in nitrogen atmosphere
Lower 1400 DEG C of pyrolytics obtain gas-phase silica；(2) activated zinc oxide, gas-phase silica, aluminium oxide and nickel salt are mixed equal
It is even to be slurried；(3) mixture obtained by making is sprayed balling-up or oil forms ball；(4) make the particle drying of step (3), drying temperature is
110-150℃；(5) microballoon of step (4) is roasted, maturing temperature is 300-550 DEG C；The absorbing desulfurization catalyst of preparation, by force
It spends, wearability is high, and what is had is desulphurizing activated, and loss of octane number is small, and operating cost is low, is very suitable to moving bed absorption desulfurization
Technique.
CN108018069A discloses a kind of sulfur-bearing hydrocarbon desulfurizing method by adsorption and device, which comprises desulfurization process:
Sulfur-bearing hydrocarbon and hydrogen donor are mixed with adsorbent, obtain the sulfur-bearing hydrocarbon of desulfurization and carry the spent agent of sulphur；Regeneration treatment: by institute
The spent agent for stating load sulphur is mixed with oxygen-containing regeneration gas, obtains regenerative agent；Reduction treatment: by the regenerative agent and reducing gas
It is mixed, obtains the reducing/regenerating agent used as sorbent circulation；Contain active metal monomer in the adsorbent, it is described to go back
The reaction condition of original place reason includes: to contain the admixture of gas of non-hydrogen reducibility gas as also Primordial Qi, reduction temperature 250
~420 DEG C, restore 0~3MPa of pressure, 50~1000h of volume space velocity of reducibility gas-1, the recovery time is 0.5~3h.The party
Method inhibits the formation of the zinc silicate in reduction reaction and desulphurization reaction, and then improves the activity and intensity of regenerative agent.
A kind of method that CN201310292325.7 discloses adsorbing and desulfurizing catalytic cracking gasoline, with urging after selective hydrodesulfurization
Change gasoline is raw material (150 μ g/g of sulfur content <), first passes through fractionating column and carries out cutting fractionation, is fractionated as light petrol and heavy petrol.
Light petrol enters fixed bed reactors and carries out non-hydrogen physical absorption desulfurization, and physical absorption desulfurization does not reduce olefin(e) centent, guarantees
The octane number of product does not lose；Heavy petrol, which enters fixed bed reactors, to carry out facing hydrogen absorption desulfurization, reaction product and light petrol object
Reason absorption desulfurization product reconciliation can reach the clean gasoline product of V sulphur index request of Europe.There are Sulfur capacity possibility for existing catalyst partially
It is low, zinc silicate easy to form, zinc aluminate are regenerated and restored, causes the reduction of adsorption activity, and due to the hair of olefin saturation
It is raw, lead to problems such as loss of octane number big.High therefore, it is necessary to develop a kind of working sulfur capacity, loss of octane number is small, regeneration and reduction
Stability is good, adsorbs desulphurizing activated high catalyst and its sulfur removal technology.
Summary of the invention
The present invention provides a kind of desulfurizing method by adsorption of catalytically cracked gasoline, and catalyst Sulfur capacity is high, and loss of octane number is small, then
Raw and Reductive stability is good, adsorbs desulphurizing activated height.
A kind of method for adsorbing and desulfurizing catalytic cracking gasoline, using fixed bed reactors, gasoline connects with absorbing desulfurization catalyst
Touching, by weight percentage, catalyst includes: the zinc oxide of 25.0-50.0wt%, the nickel oxide of 0.5-25.0wt%, 2.0-
55.0wt%ZSM-5 molecular sieve, the macroporous aluminium oxide of 20.0-50.0wt%, the cerium zirconium sosoloid of 1.0-25.0wt%；React work
Skill condition are as follows: 280-400 DEG C of reaction temperature, reaction pressure 0.4-2.5MPa, volume space velocity 3-8h-1, hydrogen to oil volume ratio 1-50.
Gasolene desulfurizing method by adsorption provided by the invention, fixed bed reactors can be fixed bed adiabatic reactor can also
To be fixed bed isothermal reactor, preferably fixed bed adiabatic reactor；Further preferably, reaction process condition are as follows: reaction temperature
280-360 DEG C, reaction pressure 0.5-2.0MPa, volume space velocity 5-8h of degree-1, hydrogen to oil volume ratio 1-40.
A kind of preparation method of catalytic gasoline absorbing desulfurization catalyst includes the following steps: (1) by nickel salt, zinc salt
It is dissolved in nitric acid, and expanding agent is added, obtain the acid solution containing nickel salt, zinc salt；(2) acid solution containing expanding agent is configured, it will
ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid are added in the acid solution containing expanding agent, stir evenly, and obtain containing ZSM-5
The mixture paste of molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid, in terms of oxide, the matter of expanding agent in the acid solution containing nickel zinc
Measure percentage composition than containing ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid mixture paste in expanding agent quality percentage
The high 2 times or more of content；Then the acid solution containing nickel salt, zinc salt is added in the slurry obtained to step (2), adds alkaline solution,
Carry out precipitation reaction；Be filtered, washed, dried after the reaction was completed, being formed, roast after obtain catalyst.
In above-mentioned method for preparing catalyst, the additional amount of expanding agent accounts for the 1- of nickel zinc oxide gross mass in step (1)
35%.
Catalyst is further improved, nickel salt, zinc salt are dissolved in deionized water, impregnate to catalyst surface, so
Catalyst is obtained by drying, roasting, controls the zinc oxide in catalyst including 25.0-50.0wt%, 0.5-25.0wt%'s
Nickel oxide.Catalyst surface nickel oxide, zinc oxide mass percentage content than catalytic inner nickel oxide, zinc oxide percentage
Content is 0.1-2.0 times high.It is desulphurizing activated and selective to be conducive to raising Catalyst Adsorption, absorption desulfurization degree is high.Again through 8-10 times
The catalyst that raw rear catalyst is desulphurizing activated and selectivity is more modified than unused nickel oxide, zinc oxide progress surface is high.
A kind of catalytic gasoline absorbing desulfurization catalyst, the quality percentage of the catalyst surface nickel oxide, zinc oxide
It is 0.1-2.0 times higher than catalytic inner nickel oxide, zinc oxide mass percentage content than content.
Further preferably, a kind of catalytic gasoline absorbing desulfurization catalyst, by weight percentage, catalyst includes:
The zinc oxide of 25.0-45.0wt%, the nickel oxide of 0.5-20.0wt%, 10.0-55.0wt%ZSM-5 molecular sieve, 20.0-
The macroporous aluminium oxide of 40.0wt%, the cerium zirconium sosoloid of 1.0-20.0wt%.
The alkaline solution includes: one of sodium bicarbonate, ammonium hydrogencarbonate, sodium carbonate, sodium hydroxide, ammonium hydroxide or several
Kind.The catalyst maturing temperature is 450-650 DEG C.
The preparation of cerium zirconium sosoloid: stoichiometrically weighing cerous nitrate, zirconium nitrate is placed in a beaker, and is configured to mix molten
Liquid adds expanding agent, in the case where being stirred continuously, to mixed solution and dripping ammonium hydroxide or carbonic acid sodium solution, carries out coprecipitated
It forms sediment and reacts, then filtered, dried, 800~950 DEG C roast 4~8 hours, then crush, are ground into powder.The addition of expanding agent
Amount accounts for the 1-30% of cerium zirconium sosoloid quality.
Expanding agent of the present invention is methylcellulose, and active carbon, polyvinyl alcohol, urea is also possible to Sodium Polyacrylate；
Polyacrylic acid；One or more of ammonium polyacrylate, preferably Sodium Polyacrylate.
Expanding agent is added in catalyst substep, and the catalyst has mesoporous, macroporous structure, nickeliferous in terms of metal oxide
The mass percentage of expanding agent is starched than the mixture containing ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid in the acid solution of zinc
The high 2 times or more of the mass percentage of expanding agent in material is conducive to the working sulfur capacity for improving absorbing desulfurization catalyst, catalyst alkene
Hydrocarbon saturation factor is low, and loss of octane number is low.
Catalyst of the present invention includes: the zinc oxide of 25.0-50.0wt%, the nickel oxide of 0.5-25.0wt%, 2.0-
55.0wt%ZSM-5 molecular sieve, the macroporous aluminium oxide of 20.0-50.0wt%, the cerium zirconium sosoloid of 1.0-25.0wt%, especially
Cerium zirconium sosoloid is introduced into and (expanding agent is added in cerium zirconium sosoloid and ZSM-5 molecular sieve, macroporous aluminium oxide mixed process), effectively
Inhibit zinc aluminate/zinc silicate generation in high temperature reduction and regenerative process, improves reduction, the regenerating stability of catalyst.This hair
Sulphur in bright suitable removing catalytically cracked gasoline, absorbing desulfurization catalyst after 8 regeneration, urge by Sulfur capacity decline 2~7%
Agent stability is good.
In order to illustrate measuring method of the present invention, by embodiment, the invention will be further elaborated, but this hair
It is bright to be not limited to these embodiments.
Specific embodiment
All raw materials of the present invention come from commercial product.
Embodiment 1
The preparation of cerium zirconium sosoloid: stoichiometrically weighing 38.8g cerous nitrate, 33.9g zirconium nitrate is placed in a beaker, and matches
Mixed solution is made, adds 4g Sodium Polyacrylate, in the case where being stirred continuously, to mixed solution and dripping ammonium hydroxide or carbonic acid
Sodium solution carries out coprecipitation reaction, is then filtered, and dries, and 840 DEG C roast 6 hours, then crush, are ground into powder.
The preparation of catalyst: (1) 67.4g nickel nitrate, 136g zinc nitrate are dissolved in nitric acid, and 16g polypropylene is added
Sour sodium obtains the acid solution containing nickel zinc；(2) acid solution of the Sodium Polyacrylate containing 5.5g is configured, 23g ZSM-5 molecular sieve, 17g is big
Porous aluminum oxide, 5.7g cerium zirconium sosoloid be added the acid solution containing Sodium Polyacrylate in, stir evenly, obtain containing ZSM-5 molecular sieve,
The mixture paste of macroporous aluminium oxide, cerium zirconium sosoloid；Then the acid solution containing nickel salt, zinc salt is added into mixture paste, then
Sodium carbonate and ammonia spirit is added, carries out precipitation reaction, obtained reaction product temperature is increased to 90 DEG C of agings 5 hours, filter,
Catalyst is obtained after washing, dry, molding, roasting.The composition of catalyst is shown in Table 1.
Embodiment 2
The preparation of cerium zirconium sosoloid in terms of metal oxide, contains with embodiment 1, the preparation step of catalyst with embodiment 1
The mass percentage of expanding agent is higher than the mixing containing ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid in the acid solution of nickel zinc
3.2 times of the mass percentage of expanding agent in object slurry, the composition of catalyst is shown in Table 1.
Embodiment 3
The preparation of cerium zirconium sosoloid is with embodiment 1, and the preparation step of catalyst is with embodiment 1, in terms of oxide, contains nickel zinc
Acid solution in expanding agent mass percentage be higher than containing ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid mixture slurry
3.8 times of the mass percentage of expanding agent in material.After obtaining catalyst, configuration nickel salt, zinc salt are dissolved in deionized water, to urging
Agent surface is impregnated, and then drying, roasting obtain the catalyst modified through nickel, zinc surface.The catalyst surface oxygen
Change nickel, the mass percentage content of zinc oxide is higher than catalytic inner nickel oxide, 0.9 times of mass percentage content of zinc oxide.
The composition of catalyst is shown in Table 1.
Embodiment 4
The preparation of cerium zirconium sosoloid is with embodiment 3, and the preparation step of catalyst is the same as embodiment 3, the catalyst surface oxygen
Change nickel, the mass percentage content of zinc oxide is higher than catalytic inner nickel oxide, 1.5 times of mass percentage content of zinc oxide.
The composition of catalyst is shown in Table 1.
1 embodiment of table/comparative example catalyst composition/wt%
| Embodiment/comparative example | Zinc oxide | Nickel oxide | ZSM-5 | Macroporous aluminium oxide | Cerium zirconium sosoloid |
| Embodiment 1 | 37 | 17.3 | 23 | 17 | 5.7 |
| Embodiment 2 | 46 | 16 | 20 | 13 | 5.0 |
| Embodiment 3 | 29 | 20 | 33 | 13.5 | 4.5 |
| Embodiment 4 | 31 | 23 | 19 | 23.5 | 3.5 |
Comparative example 1
The preparation of catalyst: (1) 67.4g nickel nitrate, 136g nitric acid zinc salt are dissolved in nitric acid, and 16g poly- third is added
Olefin(e) acid sodium obtains the acid solution containing nickel zinc；(2) acid solution for configuring the Sodium Polyacrylate containing 5.5g, by 23g ZSM-5 molecular sieve, 17g
Macroporous aluminium oxide is added in the acid solution containing Sodium Polyacrylate, stirs evenly, and obtains containing ZSM-5 molecular sieve, macroporous aluminium oxide
Mixture paste；Then the acid solution containing nickel salt, zinc salt is added into mixture paste, adds sodium carbonate and ammonia spirit, into
Row precipitation reaction, obtained reaction product temperature are increased to 90 DEG C of agings 5 hours, after being filtered, washed, dry, forming, roasting
To comparative catalyst 1.
Comparative example 2
The preparation of cerium zirconium sosoloid: stoichiometrically weighing 38.8g cerous nitrate, 33.9g zirconium nitrate is placed in a beaker, and matches
Mixed solution is made, adds 4g Sodium Polyacrylate, in the case where being stirred continuously, to mixed solution and dripping ammonium hydroxide or carbonic acid
Sodium solution carries out coprecipitation reaction, is then filtered, and dries, and 840 DEG C roast 6 hours, then crush, are ground into powder.
67.4g nickel nitrate, 136g nitric acid zinc salt: (1) being dissolved in nitric acid by the preparation of catalyst, and it is poly- that 21.5g is added
Sodium acrylate obtains the acid solution containing nickel zinc；(2) 23g ZSM-5 molecular sieve, 17g macroporous aluminium oxide, 5.7g cerium zirconium sosoloid are added
Enter in the acid solution containing nickel zinc, stir evenly, add sodium carbonate and ammonia spirit, carries out precipitation reaction, obtained reaction product
Temperature is increased to 90 DEG C of agings 5 hours, be filtered, washed, dry, forming, roast after obtain comparative catalyst 2.
Using full fraction FCC gasoline, absorbing desulfurization catalyst and comparative example catalyst are evaluated, alkene in gasoline stocks
Hydrocarbon content 38.5v%, sulfur content 127ppm, octane number 91.1.
It is evaluated using 100ml adiabatic reactor, catalyst or comparative catalyst are first restored with hydrogen, pressure
1.8MPa, bed temperature is first increased to 360 DEG C and is stopped 5 hours, then bed temperature is increased to 460 DEG C and is stopped 8 hours
Reduction terminates.Evaluating catalyst process conditions: 330 DEG C of reactor inlet temperature, pressure 1.3MPa, air speed 5.5h-1, hydrogen oil volume
Than 1.3, evaluation result is as shown in table 2.Catalyst desulfurizing rate is 90.8% or more, and loss of octane number is lower than 0.4, and working sulfur capacity is high
In 27%, alkene saturation factor is lower than 15%.1 loss of octane number of comparative catalyst is big, and 2 desulfurization degree of comparative catalyst is low, octane number
Loss is big, and working sulfur capacity is low.After absorption Sulfur capacity reaches saturation, regeneration treatment, work are carried out to catalyst or comparative catalyst
Skill condition are as follows: in a nitrogen atmosphere, with the heating rate of 35 DEG C/h, be warming up to 260 DEG C, stop 7h；Regenerated catalyst later, institute
It is the gaseous mixture of oxygen and nitrogen with regeneration gas, wherein oxygen volume content accounts for the 7% of total gas.
2 catalyst of table and comparative catalyst's reaction result
Catalyst 1 and 3 after regeneration, comparative example 1 and 2 are empty at 330 DEG C of reactor inlet temperature, pressure 1.3MPa
Fast 5.5h-1, under the conditions of hydrogen to oil volume ratio 1.3, evaluation result is as shown in table 3.Catalyst desulfurizing effect can be substantially restored to newly
Fresh dose of level effectively inhibits the generation of zinc silicate and zinc aluminate in high temperature reduction and regenerative process, improves the reduction, again of catalyst
Raw stability.The activity decline after regeneration of comparative catalyst 1 and 2, loss of octane number is big, and working sulfur capacity reduces.Again by 8 times
After life, 1 catalyst desulfurizing rate 84.1% of embodiment, Sulfur capacity decline 6%；3 catalyst desulfurizing rate 87.5% of embodiment, Sulfur capacity decline
3%.
3 catalyst of table and comparative catalyst's reaction result
| Desulfurization degree/% | Loss of octane number | Working sulfur capacity/% | |
| Embodiment 1 | 91.1 | 0.3 | 29 |
| Embodiment 3 | 92.4 | 0.3 | 31 |
| Comparative example 1 | 86.1 | 2.4 | 23 |
| Comparative example 2 | 76.9 | 1.6 | 14 |
Claims (10)
1. a kind of desulfurizing method by adsorption of catalytically cracked gasoline, which is characterized in that use fixed bed reactors, gasoline and absorption are de-
Sulfur catalyst contact, by weight percentage, catalyst includes: the zinc oxide of 25.0-50.0wt%, the oxygen of 0.5-25.0wt%
Change nickel, 2.0-55.0wt%ZSM-5 molecular sieve, the macroporous aluminium oxide of 20.0-50.0wt%, the cerium zirconium solid solution of 1.0-25.0wt%
Body；Reaction process condition are as follows: 280-400 DEG C of reaction temperature, reaction pressure 0.4-2.5MPa, volume space velocity 3-8h-1, hydrogen oil volume
Compare 1-50.
2. the desulfurizing method by adsorption of catalytically cracked gasoline according to claim 1, which is characterized in that the absorption desulphurization reaction
Process conditions are as follows: 280-360 DEG C of reaction temperature, reaction pressure 0.5-2.0MPa, volume space velocity 5-8h-1, hydrogen to oil volume ratio 1-40.
3. the desulfurizing method by adsorption of catalytically cracked gasoline according to claim 1, which is characterized in that the fixed bed reactors
It is fixed bed adiabatic reactor or fixed bed isothermal reactor.
4. the desulfurizing method by adsorption of catalytically cracked gasoline according to claim 1, which is characterized in that the catalyst surface oxygen
It is 0.1-2.0 higher than catalytic inner nickel oxide, zinc oxide mass percentage content to change nickel, the mass percentage content of zinc oxide
Times.
5. the desulfurizing method by adsorption of catalytically cracked gasoline according to claim 1, which is characterized in that the absorption desulfurization catalyst
The preparation method of agent includes the following steps: that nickel salt, zinc salt are dissolved in nitric acid by (1), and expanding agent is added, obtain containing nickel salt,
The acid solution of zinc salt；(2) acid solution containing expanding agent is configured, ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid addition are contained
It in the acid solution of expanding agent, stirs evenly, obtains the mixture slurry containing ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid
Material, in terms of oxide, the mass percentage ratio of expanding agent contains ZSM-5 molecular sieve, macroporous aluminium oxide, cerium in the acid solution containing nickel zinc
The high 2 times or more of the mass percentage of expanding agent in the mixture paste of zirconium solid solution；Then in the slurry obtained to step (2)
The acid solution containing nickel salt, zinc salt is added, adds alkaline solution, carries out precipitation reaction；Be filtered, washed, dried after the reaction was completed,
Catalyst is obtained after molding, roasting.
6. the desulfurizing method by adsorption of catalytically cracked gasoline according to claim 4, which is characterized in that the absorption desulfurization catalyst
The preparation method of agent includes the following steps: that nickel salt, zinc salt are dissolved in nitric acid by (1), and expanding agent is added, obtain containing nickel salt,
The acid solution of zinc salt；(2) acid solution containing expanding agent is configured, ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid addition are contained
It in the acid solution of expanding agent, stirs evenly, obtains the mixture slurry containing ZSM-5 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid
Material, in terms of oxide, the mass percentage ratio of expanding agent contains ZSM-5 molecular sieve, macroporous aluminium oxide, cerium in the acid solution containing nickel zinc
The high 2 times or more of the mass percentage of expanding agent in the mixture paste of zirconium solid solution；Then in the slurry obtained to step (2)
The acid solution containing nickel salt, zinc salt is added, adds alkaline solution, carries out precipitation reaction；Be filtered, washed, dried after the reaction was completed,
Catalyst is obtained after molding, roasting；Then be further improved to catalyst: nickel salt, zinc salt are dissolved in deionized water, to catalysis
Agent surface is impregnated, and then drying, roasting obtain finished catalyst, and controlling includes 25.0-50.0wt%'s in catalyst
Zinc oxide, the nickel oxide of 0.5-25.0wt%.
7. according to the desulfurizing method by adsorption of any one of claim 5 or 6 catalytically cracked gasoline, which is characterized in that the cerium
The preparation process of zirconium solid solution is as follows: stoichiometrically weighing cerous nitrate, zirconium nitrate is placed in a beaker, is configured to mix molten
Liquid adds expanding agent, in the case where being stirred continuously, to mixed solution and dripping ammonium hydroxide or carbonic acid sodium solution, carries out coprecipitated
It forms sediment and reacts, then filtered, dried, 800~950 DEG C of 4~8h of roasting, then crush, be ground into powder.
8. according to the desulfurizing method by adsorption of any one of claim 5 or 6 catalytically cracked gasoline, which is characterized in that the alkali
Property solution include: one or more of sodium bicarbonate, ammonium hydrogencarbonate, sodium carbonate, sodium hydroxide, ammonium hydroxide, the catalyst roasting
Burning temperature is 450-650 DEG C.
9. according to the desulfurizing method by adsorption of any one of claim 5 or 6 catalytically cracked gasoline, which is characterized in that the step
Suddenly the additional amount of expanding agent accounts for the 1-35% of nickel zinc oxide gross mass in (1).
10. according to the desulfurizing method by adsorption of any one of claim 5 or 6 catalytically cracked gasoline, which is characterized in that the expansion
Hole agent is one or more of Sodium Polyacrylate, polyacrylic acid, ammonium polyacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811347239.0A CN109207192B (en) | 2018-11-13 | 2018-11-13 | Adsorption desulfurization method for catalytically cracked gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811347239.0A CN109207192B (en) | 2018-11-13 | 2018-11-13 | Adsorption desulfurization method for catalytically cracked gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109207192A true CN109207192A (en) | 2019-01-15 |
| CN109207192B CN109207192B (en) | 2020-12-18 |
Family
ID=64996041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811347239.0A Active CN109207192B (en) | 2018-11-13 | 2018-11-13 | Adsorption desulfurization method for catalytically cracked gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109207192B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433817A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Desulphurization sorbent |
| CN101481627A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbing agent and use method thereof |
| CN101773815A (en) * | 2009-01-08 | 2010-07-14 | 中国石油化工股份有限公司 | silicate-resistant desulfurization sorbent |
| CN101940908A (en) * | 2009-07-08 | 2011-01-12 | 中国石油化工股份有限公司 | Ultra-deep absorption desulfurizer for light oil and application thereof |
| CN102029140A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Desulfurizing agent with nuclear/shell structure and preparation method |
| CN103240117A (en) * | 2013-05-17 | 2013-08-14 | 中国石油大学(北京) | Gasoline desulfurization catalyst and preparation method thereof and gasoline desulfurization method |
| CN104415775A (en) * | 2013-08-21 | 2015-03-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method and application thereof |
| CN108722168A (en) * | 2018-06-15 | 2018-11-02 | 西南化工研究设计院有限公司 | A kind of renewable dry flue gas desulphurization agent and its preparation method and application |
-
2018
- 2018-11-13 CN CN201811347239.0A patent/CN109207192B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433817A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Desulphurization sorbent |
| CN101481627A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbing agent and use method thereof |
| CN101773815A (en) * | 2009-01-08 | 2010-07-14 | 中国石油化工股份有限公司 | silicate-resistant desulfurization sorbent |
| CN101940908A (en) * | 2009-07-08 | 2011-01-12 | 中国石油化工股份有限公司 | Ultra-deep absorption desulfurizer for light oil and application thereof |
| CN102029140A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Desulfurizing agent with nuclear/shell structure and preparation method |
| CN103240117A (en) * | 2013-05-17 | 2013-08-14 | 中国石油大学(北京) | Gasoline desulfurization catalyst and preparation method thereof and gasoline desulfurization method |
| CN104415775A (en) * | 2013-08-21 | 2015-03-18 | 中国石油化工股份有限公司 | Desulphurization catalyst and preparation method and application thereof |
| CN108722168A (en) * | 2018-06-15 | 2018-11-02 | 西南化工研究设计院有限公司 | A kind of renewable dry flue gas desulphurization agent and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109207192B (en) | 2020-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1259776A (en) | Selective removal of hydrogen sulfide over zinc titanate and alumina | |
| CN102430412B (en) | Method for preparing desulfurizer capable of absorbing catalytic cracking gas at high selection | |
| CN105728027B (en) | Adsorption desulfurization catalyst and preparation method thereof | |
| CN101619231B (en) | Fuel oil adsorption desulfurization adsorbent and method for preparing same | |
| CN104667861B (en) | A kind of sulfur method of the desulfuration adsorbent for gasoline and gasoline | |
| WO2021063345A1 (en) | Dearsenification adsorbent and preparation method therefor | |
| CN103240117A (en) | Gasoline desulfurization catalyst and preparation method thereof and gasoline desulfurization method | |
| US6723230B1 (en) | Regeneration of iron-based hydrogen sulfide sorbents | |
| RU2361668C2 (en) | Method of producing catalyst for desulphuration of hydrocarbon streams | |
| CN109370646A (en) | Catalytically cracked gasoline desulfurization method for modifying | |
| CN109486509A (en) | A kind of absorbing desulfurization catalyst and preparation method thereof | |
| CN109370645A (en) | A kind of modifying catalytically cracked gasoline method | |
| CN109486508A (en) | A kind of FCC gasoline desulfurizing method by adsorption | |
| CN109486523A (en) | A kind of FCC gasoline desulfurization method for modifying | |
| CN109207192A (en) | The desulfurizing method by adsorption of catalytically cracked gasoline | |
| CN109364985A (en) | A kind of catalytic gasoline absorbing desulfurization catalyst and preparation method thereof | |
| CN109370638A (en) | The desulfurizing method by adsorption of FCC gasoline | |
| CN101724433B (en) | Method for adsorbing and desulfurizing catalytic cracking gasoline | |
| JP2007160250A (en) | Method of manufacturing catalyst, catalytic cracking catalyst and method of producing low-sulfur catalytically-cracked gasoline | |
| CN109504425A (en) | A kind of gasolene desulfurizing method by adsorption | |
| CN102744073B (en) | Preparation method of gasoline desulfurization microsphere catalyst | |
| JP4519379B2 (en) | Heavy hydrocarbon oil hydrotreating catalyst | |
| CN113262795B (en) | Catalyst for hydrogenation dearsenification and desulfurization of naphtha and preparation method thereof | |
| CN112657459B (en) | Light gasoline desulfurization adsorbent, preparation method thereof and light gasoline desulfurization method | |
| CN101905161B (en) | Adsorption desulfurization catalyst for catalytically cracked gasoline, preparation 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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20201201 Address after: 201507 Shanghai City, Jinshan District Caojing town Yuegong Road No. 288 Applicant after: SHANGHAI YOUHAO TECHNOLOGY Co.,Ltd. Address before: 362100 Chenzhuang 123, Jinta Village, Quangang District, Quanzhou City, Fujian Province Applicant before: Chen Kailong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |