CN109486509A - A kind of absorbing desulfurization catalyst and preparation method thereof - Google Patents
A kind of absorbing desulfurization catalyst and preparation method thereof Download PDFInfo
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- CN109486509A CN109486509A CN201811347306.9A CN201811347306A CN109486509A CN 109486509 A CN109486509 A CN 109486509A CN 201811347306 A CN201811347306 A CN 201811347306A CN 109486509 A CN109486509 A CN 109486509A
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- catalyst
- oxide
- zinc
- molybdenum
- salt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 42
- 230000023556 desulfurization Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 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
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 17
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 16
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 15
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 150000002751 molybdenum Chemical class 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000011259 mixed solution 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
- 230000032683 aging Effects 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000004898 kneading Methods 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 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
- 235000019738 Limestone Nutrition 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 abstract description 23
- 239000011593 sulfur Substances 0.000 abstract description 23
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 17
- 230000008929 regeneration Effects 0.000 abstract description 13
- 238000011069 regeneration method Methods 0.000 abstract description 13
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- 230000009467 reduction Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000001172 regenerating effect Effects 0.000 description 9
- 230000003009 desulfurizing effect Effects 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- -1 zinc aluminate Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 230000008859 change Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WJPZDRIJJYYRAH-UHFFFAOYSA-N [Zn].[Mo] Chemical compound [Zn].[Mo] WJPZDRIJJYYRAH-UHFFFAOYSA-N 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-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 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- MFPOUZMIWRBOON-UHFFFAOYSA-N [Mo].[Co].[Zn] Chemical compound [Mo].[Co].[Zn] MFPOUZMIWRBOON-UHFFFAOYSA-N 0.000 description 1
- NTEBCQWNOKBHIV-UHFFFAOYSA-N [O-2].[Zn+2].[Mo+4].[Co+2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Zn+2].[Mo+4].[Co+2].[O-2].[O-2].[O-2] NTEBCQWNOKBHIV-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium 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
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 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
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 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
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
Abstract
The present invention relates to a kind of absorbing desulfurization catalyst and preparation methods, by weight percentage, catalyst includes: the zinc oxide of 25.0-50.0wt%, the cobalt oxide and/or molybdenum oxide of 1.0-15.0wt%, 2.0-55.0wt%SAPO-11 molecular sieve, the macroporous aluminium oxide of 1.0-20.0wt%, the silica of 1.0-25.0wt%, the cerium zirconium sosoloid of 1.0-25.0wt%.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 absorbing desulfurization catalysts and preparation method thereof, are specifically used for gasoline fraction and adsorb desulfurization.
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, 0~3MPa of pressure, 50~1000h-1 of volume space velocity of reducibility gas are restored, the recovery time is 0.5~3h.It should
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, and regeneration and Reductive stability are good, adsorbs desulfurization
The high catalyst of activity.
Summary of the invention
The present invention provides a kind of absorbing desulfurization catalyst and preparation method, and catalyst Sulfur capacity is high, and loss of octane number is small, regeneration
And Reductive stability is good, adsorbs desulphurizing activated height.
A kind of absorbing desulfurization catalyst, by weight percentage, catalyst include: the zinc oxide of 25.0-50.0wt%,
The cobalt oxide and/or molybdenum oxide of 1.0-15.0wt%, 2.0-55.0wt%SAPO-11 molecular sieve, the macropore of 1.0-20.0wt%
Aluminium oxide, the silica of 1.0-25.0wt%, the cerium zirconium sosoloid of 1.0-25.0wt%.
The preparation method of above-mentioned catalyst includes the following steps: that cobalt salt and/or molybdenum salt, zinc salt are dissolved in nitric acid by (1)
In, and expanding agent is added, obtain the acid solution of the zinc of molybdenum containing cobalt；(2) acid solution containing expanding agent is configured, by SAPO-11 molecular sieve, greatly
Porous aluminum oxide, cerium zirconium sosoloid are added in the acid solution containing expanding agent, stir evenly, obtain molecular sieve containing SAPO-11, macropore oxygen
Change the mixture paste of aluminium, cerium zirconium sosoloid；Then the acid solution containing cobalt salt and/or molybdenum salt, zinc salt is added into mixture paste,
Alkaline solution is added, precipitation reaction, obtained reaction product aging 2-5 hours, after being filtered, washed, dried, being crushed are carried out
Coprecipitated powder is obtained, the silicon source containing expanding agent is added, roasting obtains finished catalyst after kneading and compacting.
The silicon source is one or both of silica gel, lime stone, sodium metasilicate, silicon powder, diatomite.Expand in step (1)
The additional amount of hole agent accounts for the 1-35% of cobalt molybdenum zinc oxide gross mass.The additional amount of expanding agent accounts for the 1- of silicon source quality in silicon source
30%.
Further preferably, a kind of absorbing desulfurization catalyst, by weight percentage, catalyst include: 25.0-40.0wt%
Zinc oxide, the cobalt oxide and/or molybdenum oxide of 5.0-15.0wt%, 10.0-50.0wt%SAPO-11 molecular sieve, 10.0-
The macroporous aluminium oxide of 20.0wt%, the silica of 5.0-25.0wt%, the cerium zirconium sosoloid of 4.0-25.0wt%.
Catalyst is further improved, cobalt salt is configured and/or molybdenum salt, zinc salt is dissolved in acid, catalyst surface is carried out
Dipping, then drying, roasting obtain catalyst, wherein the matter of the catalyst surface cobalt oxide and/or molybdenum oxide, zinc oxide
It is 0.05-1.5 times higher than the mass percentage content of catalytic inner cobalt oxide and/or molybdenum oxide, zinc oxide to measure degree,
Control the zinc oxide in catalyst including 25.0-50.0wt%, the cobalt oxide and/or molybdenum oxide of 1.0-15.0wt%.And then it mentions
High catalyst absorption is desulphurizing activated and selective, and absorption desulfurization degree is high.Through 8-10 regenerated catalyst it is desulphurizing activated and selection
Property than unused cobalt oxide and/or molybdenum oxide, zinc oxide to carry out the modified catalyst in surface high.
A kind of absorbing desulfurization catalyst, the mass percent of the catalyst surface cobalt oxide and/or molybdenum oxide, zinc oxide
Content is 0.05-1.5 times higher than the mass percentage content of catalytic inner cobalt oxide and/or molybdenum oxide, zinc oxide.
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, in terms of metal oxide, contains cobalt
In the acid solution of molybdenum zinc the mass percentage of expanding agent be higher than molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid it is mixed
The mass percentage 2 times or more for closing expanding agent in object slurry is conducive to the working sulfur capacity for improving absorbing desulfurization catalyst, catalysis
Agent alkene saturation factor is low, and loss of octane number is low.
Catalyst of the present invention contains the zinc oxide of 25.0-50.0wt%, the cobalt oxide of 1.0-15.0wt% and/or oxidation
Molybdenum, 2.0-55.0wt%SAPO-11 molecular sieve, the macroporous aluminium oxide of 1.0-20.0wt%, the silica of 1.0-25.0wt%,
Introducing (cerium zirconium sosoloid and the ZSM-5 molecular sieve, macropore of the cerium zirconium sosoloid of 1.0-25.0wt%, especially cerium zirconium sosoloid
Expanding agent is added in aluminium oxide mixed process), effectively inhibit the generation of zinc silicate and zinc aluminate in high temperature reduction and regenerative process,
Improve reduction, the regenerating stability of catalyst.The present invention is suitble to remove the sulphur in catalytically cracked gasoline, and catalyst passes through 8 times again
After life, Sulfur capacity decline 2~6%, catalyst 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.
70.4g ammonium molybdate, 149g zinc nitrate, 15.5g cobalt nitrate: (1) being dissolved in nitric acid by the preparation of catalyst, and adds
Enter 22g Sodium Polyacrylate, obtains the acid solution of the zinc of molybdenum containing cobalt；(2) acid solution for configuring the Sodium Polyacrylate containing 7g, by 11g SAPO-
11 molecular sieves, 19g macroporous aluminium oxide, 4.8g cerium zirconium sosoloid are added in the acid solution containing Sodium Polyacrylate, stir evenly, obtain
The mixture paste of molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid；Then it is added into mixture paste and contains cobalt
The acid solution of salt and molybdenum salt, zinc salt adds sodium carbonate and ammonia spirit, carries out precipitation reaction, obtained reaction product temperature liter
Up to 90 DEG C aging 5 hours, be filtered, washed, dried, crush after obtain coprecipitated powder, add containing Sodium Polyacrylate
Silica solution, roasting obtains finished catalyst after kneading and compacting.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
In the acid solution of molybdenum zinc the mass percentage of expanding agent be higher than molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid it is mixed
3 times of mass percentage for closing expanding agent in object slurry, the composition of catalyst is shown in Table 1.
Embodiment 3
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 molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid in the acid solution of cobalt molybdenum zinc
3.5 times of the mass percentage of expanding agent in mixture paste.After obtaining catalyst, configures cobalt salt and molybdenum salt, zinc salt are dissolved in
In dust technology, catalyst surface is impregnated, then drying, roasting obtain surface-modified catalyst.The catalysis
Agent surface oxidation cobalt, molybdenum oxide, zinc oxide mass percentage content be higher than catalytic inner cobalt oxide and molybdenum oxide, zinc oxide
0.8 times of mass percentage content.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 cobalt, molybdenum oxide, zinc oxide mass percentage content be higher than catalytic inner cobalt oxide and molybdenum oxide, zinc oxide quality hundred
Divide than 1.4 times of content.The composition of catalyst is shown in Table 1.
1 embodiment of table/comparative example catalyst composition/wt%
Comparative example 1
70.4g ammonium molybdate, 149g zinc nitrate, 15.5g cobalt nitrate: (1) being dissolved in nitric acid by the preparation of catalyst, and adds
Enter 22g Sodium Polyacrylate, obtains the acid solution of the zinc of molybdenum containing cobalt；(2) acid solution for configuring the Sodium Polyacrylate containing 7g, by 11g SAPO-
11 molecular sieves, 19g macroporous aluminium oxide are added in the acid solution containing Sodium Polyacrylate, stir evenly, obtain molecule containing SAPO-11
The mixture paste of sieve, macroporous aluminium oxide, cerium zirconium sosoloid；Then it is added into mixture paste and contains cobalt salt and molybdenum salt, zinc salt
Acid solution, add sodium carbonate and ammonia spirit, carry out precipitation reaction, obtained reaction product temperature is increased to 90 DEG C of agings 5
Hour, be filtered, washed, dried, crush after obtain coprecipitated powder, add the silica solution containing Sodium Polyacrylate, kneading at
Roasting obtains comparative catalyst 1 after type.
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.
The preparation of catalyst: (1) 70.4g ammonium molybdate, 149g zinc nitrate, 15.5g cobalt nitrate are dissolved in nitric acid, are obtained
The acid solution of the zinc of molybdenum containing cobalt；(2) acid solution is configured, by 11g SAPO-11 molecular sieve, 19g macroporous aluminium oxide, 4.8g cerium zirconium sosoloid
It is added in the acid solution containing Sodium Polyacrylate, stirs evenly, obtain molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid
Mixture paste；Then the acid solution containing cobalt salt and molybdenum salt, zinc salt is added into mixture paste, adds 29g polyacrylic acid
Then sodium adds sodium carbonate and ammonia spirit, carry out precipitation reaction, and obtained reaction product temperature is increased to 90 DEG C of agings 5
Hour, be filtered, washed, dried, crush after obtain coprecipitated powder, add the silica solution containing Sodium Polyacrylate, kneading at
Roasting obtains comparative catalyst 2 after type.
Using full fraction FCC gasoline, absorbing desulfurization catalyst and comparative example catalyst are evaluated, alkene in gasoline stocks
Hydrocarbon content 32.3v%, sulfur content 156ppm, octane number 89.9.
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: 320 DEG C of reactor inlet temperature, pressure 1.1MPa, air speed 5.0h-1, hydrogen oil volume
Than 1.0, evaluation result is as shown in table 2.Catalyst desulfurizing rate is 89.2% or more, and loss of octane number is lower than 0.4, and working sulfur capacity is high
In 28%, 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 the 7% of the total gas of oxygen volume content Zhan.
2 catalyst of table and comparative catalyst's reaction result
| Desulfurization degree/% | Loss of octane number | Working sulfur capacity/% | |
| Embodiment 1 | 90.1 | 0.3 | 30 |
| Embodiment 2 | 89.2 | 0.4 | 28 |
| Embodiment 3 | 91.4 | 0.3 | 29 |
| Embodiment 4 | 91.9 | 0.2 | 32 |
| Comparative example 1 | 89.6 | 1.6 | 28 |
| Comparative example 2 | 86.7 | 1.1 | 18 |
Catalyst 1 and 4 after regeneration, comparative example 1 and 2 are empty at 320 DEG C of reactor inlet temperature, pressure 1.1MPa
Fast 5.0h-1, under the conditions of hydrogen to oil volume ratio 1.0, 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 85.3% of embodiment, Sulfur capacity decline 5%；4 catalyst desulfurizing rate 88.4% of embodiment, Sulfur capacity decline
2%.
3 catalyst of table and comparative catalyst's reaction result
| Desulfurization degree/% | Loss of octane number | Working sulfur capacity/% | |
| Embodiment 1 | 90.0 | 0.4 | 29 |
| Embodiment 4 | 91.8 | 0.3 | 31 |
| Comparative example 1 | 87.4 | 2.5 | 23 |
| Comparative example 2 | 76.7 | 1.8 | 16 |
Claims (10)
1. a kind of absorbing desulfurization catalyst, which is characterized in that by weight percentage, catalyst includes: 25.0-50.0wt%'s
Zinc oxide, the cobalt oxide and/or molybdenum oxide of 1.0-15.0wt%, 2.0-55.0wt%SAPO-11 molecular sieve, 1.0-20.0wt%
Macroporous aluminium oxide, the silica of 1.0-25.0wt%, the cerium zirconium sosoloid of 1.0-25.0wt%.
2. absorbing desulfurization catalyst according to claim 1, which is characterized in that the catalyst surface cobalt oxide and/or
Molybdenum oxide, zinc oxide mass percentage content than catalytic inner cobalt oxide and/or molybdenum oxide, zinc oxide mass percent
Content is 0.05-1.5 times high.
3. absorbing desulfurization catalyst according to claim 1, which is characterized in that by weight percentage, the catalyst
It include: the zinc oxide of 25.0-40.0wt%, the cobalt oxide and/or molybdenum oxide of 5.0-15.0wt%, 10.0-50.0wt%SAPO-
The cerium zirconium of 11 molecular sieves, the macroporous aluminium oxide of 10.0-20.0wt%, the silica of 5.0-25.0wt%, 4.0-25.0wt% is solid
Solution.
4. a kind of preparation method of absorbing desulfurization catalyst described in claim 1, which comprises the steps of: (1) will
Cobalt salt and/or molybdenum salt, zinc salt are dissolved in nitric acid, and expanding agent is added, and obtain the acid solution of the zinc of molybdenum containing cobalt；(2) configuration contains reaming
SAPO-11 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid are added in the acid solution containing expanding agent the acid solution of agent, and stirring is equal
It is even, obtain the mixture paste of molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid, reaming in the acid solution of the zinc of molybdenum containing cobalt
The mass percentage of agent is higher than expanding agent in the mixture paste of molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid
Mass percentage 2 times or more；Then the acid solution containing cobalt salt and/or molybdenum salt, zinc salt is added into mixture paste, adds
Alkaline solution, carry out precipitation reaction, obtained reaction product aging 2-5 hours, be filtered, washed, dried, crush after be total to
Powder is precipitated, the silicon source containing expanding agent is added, roasting obtains finished catalyst after kneading and compacting.
5. the preparation method of absorbing desulfurization catalyst according to claim 2, which comprises the steps of: (1) will
Cobalt salt and/or molybdenum salt, zinc salt are dissolved in nitric acid, and expanding agent is added, and obtain the acid solution of the zinc of molybdenum containing cobalt；(2) configuration contains reaming
SAPO-11 molecular sieve, macroporous aluminium oxide, cerium zirconium sosoloid are added in the acid solution containing expanding agent the acid solution of agent, and stirring is equal
It is even, obtain the mixture paste of molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid, reaming in the acid solution of the zinc of molybdenum containing cobalt
The mass percentage of agent is higher than expanding agent in the mixture paste of molecular sieve containing SAPO-11, macroporous aluminium oxide, cerium zirconium sosoloid
Mass percentage 2 times or more；Then the acid solution containing cobalt salt and/or molybdenum salt, zinc salt is added into mixture paste, adds
Alkaline solution, carry out precipitation reaction, obtained reaction product aging 2-5 hours, be filtered, washed, dried, crush after be total to
Powder is precipitated, the silicon source containing expanding agent is added, roasting obtains catalyst after kneading and compacting；Then catalyst is further changed
Into: configuration cobalt salt and/or molybdenum salt, zinc salt are dissolved in acid, are impregnated to catalyst surface, and then drying, roasting obtain
Finished catalyst.
6. according to the preparation method of any one of claim 4 or 5 absorbing desulfurization catalyst, which is characterized in that the silicon source
It is one or both of silica gel, lime stone, sodium metasilicate, silicon powder, diatomite.
7. according to the preparation method of any one of claim 4 or 5 absorbing desulfurization catalyst, which is characterized in that the alkalinity
Solution includes: one or more of sodium bicarbonate, ammonium hydrogencarbonate, sodium carbonate, sodium hydroxide, ammonium hydroxide, the catalyst roasting
Temperature is 450-650 DEG C.
8. according to the preparation method of any one of claim 4 or 5 absorbing desulfurization catalyst, which is characterized in that the cerium zirconium
The preparation process of solid solution is as follows: it stoichiometrically weighs cerous nitrate, zirconium nitrate is placed in a beaker, is configured to mixed solution,
Expanding agent is added, in the case where being stirred continuously, to mixed solution and dripping ammonium hydroxide or carbonic acid sodium solution, be co-precipitated anti-
It answers, is then filtered, dried, 800~950 DEG C of 4~8h of roasting, then crush, be ground into powder.The additional amount of expanding agent accounts for cerium zirconium
It is dissolved the 1-30% of weight.
9. according to the preparation method of any one of claim 4 or 5 absorbing desulfurization catalyst, which is characterized in that the reaming
Agent is one or more of methylcellulose, active carbon, polyvinyl alcohol or urea.
10. according to the preparation method of any one of claim 4 or 5 absorbing desulfurization catalyst, which is characterized in that the reaming
Agent is one or more of Sodium Polyacrylate, polyacrylic acid, ammonium polyacrylate.
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