CN109486509B - Adsorption desulfurization catalyst and preparation method thereof - Google Patents
Adsorption desulfurization catalyst and preparation method thereof Download PDFInfo
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- CN109486509B CN109486509B CN201811347306.9A CN201811347306A CN109486509B CN 109486509 B CN109486509 B CN 109486509B CN 201811347306 A CN201811347306 A CN 201811347306A CN 109486509 B CN109486509 B CN 109486509B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 49
- 230000023556 desulfurization Effects 0.000 title claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000006104 solid solution Substances 0.000 claims abstract description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 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 21
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 19
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 19
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 18
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 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 16
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 16
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 16
- 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 16
- 239000002002 slurry Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 150000002751 molybdenum Chemical class 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000000274 adsorptive effect Effects 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000012670 alkaline solution 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
- 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
- 229920002125 Sokalan® Polymers 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
- 239000004202 carbamide 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
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide 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
- 239000005909 Kieselgur Substances 0.000 claims 1
- 239000003637 basic solution Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 abstract description 25
- 239000011593 sulfur Substances 0.000 abstract description 25
- 230000008929 regeneration Effects 0.000 abstract description 18
- 238000011069 regeneration method Methods 0.000 abstract description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 17
- 230000035515 penetration Effects 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000012492 regenerant Substances 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000004110 Zinc silicate Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000002994 raw material 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- -1 zinc aluminate Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000010438 heat treatment 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
- 230000000149 penetrating effect Effects 0.000 description 2
- 235000019738 Limestone Nutrition 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to an adsorption desulfurization catalyst and a preparation method thereof, wherein the catalyst comprises the following components in percentage by weight: 25.0-50.0 wt% of zinc oxide, 1.0-15.0 wt% of cobalt oxide and/or molybdenum oxide, 2.0-55.0 wt% of SAPO-11 molecular sieve, 1.0-20.0 wt% of macroporous alumina, 1.0-25.0 wt% of silicon oxide and 1.0-25.0 wt% of cerium-zirconium solid solution. The catalyst has high sulfur penetration capacity, small octane value loss and good regeneration and reduction stability.
Description
Technical Field
The invention relates to an adsorption desulfurization catalyst and a preparation method thereof, and particularly relates to an adsorption desulfurization catalyst for gasoline fraction.
Background
The gasoline adsorption desulfurization technology becomes an important means for upgrading the quality of oil products, and the technology has the characteristics of high sulfur selectivity, small octane value loss and low investment and operation cost. Most of the existing adsorbents are desulfurization adsorbents prepared by using a silicon/aluminum material as a carrier and zinc oxide/active metal (such as nickel) as an active component, and the adsorption activity is reduced due to the formation of carbon deposit, zinc sulfide, zinc silicate and zinc aluminate in the reaction process, so that the regeneration reduction is needed to recover the activity of the adsorbent. The octane number loss is large due to the occurrence of olefin saturation.
The existing gasoline adsorption desulfurization method mainly comprises the following steps: (1) and (3) desulfurization treatment: mixing and contacting sulfur-containing hydrocarbon and hydrogen donor with an adsorbent to obtain desulfurized sulfur-containing hydrocarbon and a sulfur-carrying spent catalyst; (2) regeneration treatment: mixing and contacting the sulfur-carrying spent regenerant with oxygen-containing regeneration gas to obtain a regenerant; (3) reduction treatment: mixing and contacting the regenerant with a reducing gas to obtain a reducing regenerant which is recycled as an adsorbent; and refluxing the reduction regenerant obtained in the step (3) as an adsorbent to the step (1) to form an adsorbent circulating flow path. With continuous cyclic reduction and regeneration of the adsorbent, the adsorbent often has the problems of fragmentation (strength reduction) and activity reduction, and further the desulfurization efficiency is reduced.
CN103657709A discloses a reactive adsorption desulfurization-aromatization reaction process and a catalyst thereof. The catalyst not only has the function of reaction adsorption desulfurization when the catalytic cracking gasoline raw material is hydrotreated, but also can be coupled with the reaction adsorption desulfurization reaction and the aromatization reaction, so that the octane number of the product is not obviously reduced while deep desulfurization can be achieved when the developed process and the catalyst thereof modify the catalytic cracking gasoline raw material. The FCC gasoline with the sulfur content of 300-800ppm is used as the raw material, the S content of the product gasoline is less than 10ppm, the olefin content is reduced by 10 percent, the RON loss is less than 1, and the gasoline yield is more than 95 percent. CN101905161A relates to a catalytic gasoline adsorption desulfurization catalyst and preparation and application thereof; the weight percentage composition is as follows: 10-85% of active zinc oxide, 5-80% of white carbon black, 5-30% of alumina and 4-45% of nickel oxide; (1) carrying out pyrolysis on titanium tetrachloride at 1400 ℃ under hydrogen atmosphere to obtain fumed silica; (2) mixing active zinc oxide, fumed silica, alumina and nickel salt uniformly to form slurry; (3) spraying the mixture into balls or injecting oil into balls; (4) drying the particles in the step (3), wherein the drying temperature is 110-150 ℃; (5) roasting the microspheres obtained in the step (4) at the roasting temperature of 300-550 ℃; the prepared adsorption desulfurization catalyst has the advantages of good strength, high wear resistance, good desulfurization activity, small octane number loss and low operation cost, and is very suitable for a moving bed adsorption desulfurization process.
CN108018069A discloses a sulfur-containing hydrocarbon adsorption desulfurization method and device, the method comprises: and (3) desulfurization treatment: mixing and contacting sulfur-containing hydrocarbon and hydrogen donor with an adsorbent to obtain desulfurized sulfur-containing hydrocarbon and a sulfur-carrying spent catalyst; regeneration treatment: mixing and contacting the sulfur-carrying spent regenerant with oxygen-containing regeneration gas to obtain a regenerant; reduction treatment: mixing and contacting the regenerant with a reducing gas to obtain a reducing regenerant which is recycled as an adsorbent; the adsorbent contains active metal monomers, and the reaction conditions of the reduction treatment comprise: a gas mixture containing non-hydrogen reducing gas is used as reducing gas, the reducing temperature is 250-420 ℃, the reducing pressure is 0-3 MPa, the volume space velocity of the reducing gas is 50-1000 h < -1 >, and the reducing time is 0.5-3 h. The method suppresses the formation of zinc silicate in the reduction reaction and desulfurization reaction, thereby improving the activity and strength of the regenerant. CN201310292325.7 discloses a method for adsorption desulfurization of catalytically cracked gasoline, which comprises the steps of using the catalytic gasoline subjected to selective hydrodesulfurization as a raw material (the sulfur content is less than 150 mu g/g), and performing cutting fractionation by a fractionating tower to obtain light gasoline and heavy gasoline. The light gasoline enters a fixed bed reactor to be subjected to non-hydrogenation physical adsorption desulfurization, the olefin content is not reduced by the physical adsorption desulfurization, and the octane number of the product is not lost; the heavy gasoline enters a fixed bed reactor to be subjected to hydro-adsorption desulfurization, and the reaction product is blended with the light gasoline physical adsorption desulfurization product to obtain a clean gasoline product which can meet the Euro V sulfur index requirement. The prior catalyst has the problems that the sulfur capacity is possibly low, zinc silicate and zinc aluminate are easily formed during regeneration and reduction, the adsorption activity is reduced, the octane number loss is large due to the occurrence of olefin saturation reaction, and the like.
Therefore, it is necessary to develop a catalyst with high breakthrough sulfur capacity, low octane number loss, good regeneration and reduction stability, and high adsorption desulfurization activity.
Disclosure of Invention
The invention provides an adsorption desulfurization catalyst and a preparation method thereof, and the catalyst has the advantages of high sulfur capacity, small octane value loss, good regeneration and reduction stability and high adsorption desulfurization activity.
An adsorptive desulfurization catalyst comprising, in weight percent: 25.0-50.0 wt% of zinc oxide, 1.0-15.0 wt% of cobalt oxide and/or molybdenum oxide, 2.0-55.0 wt% of SAPO-11 molecular sieve, 1.0-20.0 wt% of macroporous alumina, 1.0-25.0 wt% of silicon oxide and 1.0-25.0 wt% of cerium-zirconium solid solution.
The preparation method of the catalyst comprises the following steps: (1) dissolving cobalt salt and/or molybdenum salt and zinc salt in nitric acid, and adding a pore-expanding agent to obtain acid liquor containing cobalt, molybdenum and zinc; (2) preparing an acid solution containing a pore-expanding agent, adding the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution into the acid solution containing the pore-expanding agent, and uniformly stirring to obtain a mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution; and then adding acid liquor containing cobalt salt and/or molybdenum salt and zinc salt into the mixture slurry, adding alkaline solution, carrying out precipitation reaction, aging the obtained reaction product for 2-5 hours, filtering, washing, drying and crushing to obtain coprecipitation powder, adding a silicon source containing a pore-expanding agent, kneading, molding and roasting to obtain the finished catalyst.
The silicon source is one or two of silica gel, limestone, sodium silicate, silica micropowder and diatomite. The addition amount of the pore-expanding agent in the step (1) accounts for 1-35% of the total mass of the cobalt, molybdenum and zinc oxide. The addition amount of the pore-expanding agent in the silicon source accounts for 1-30% of the mass of the silicon source.
Further preferably, the adsorption desulfurization catalyst comprises the following components in percentage by weight: 25.0-40.0 wt% of zinc oxide, 5.0-15.0 wt% of cobalt oxide and/or molybdenum oxide, 10.0-50.0 wt% of SAPO-11 molecular sieve, 10.0-20.0 wt% of macroporous alumina, 5.0-25.0 wt% of silicon oxide and 4.0-25.0 wt% of cerium-zirconium solid solution.
The catalyst is further improved, cobalt salt and/or molybdenum salt and zinc salt are prepared to be dissolved in acid, the surface of the catalyst is soaked, and then the catalyst is obtained by drying and roasting, wherein the mass percentage content of cobalt oxide and/or molybdenum oxide and zinc oxide on the surface of the catalyst is 0.05-1.5 times higher than that of cobalt oxide and/or molybdenum oxide and zinc oxide in the catalyst, and the catalyst is controlled to comprise 25.0-50.0 wt% of zinc oxide and 1.0-15.0 wt% of cobalt oxide and/or molybdenum oxide. Further improving the adsorption desulfurization activity and selectivity of the catalyst and having high adsorption desulfurization rate. The desulfurization activity and selectivity of the catalyst after 8-10 times of regeneration are higher than those of the catalyst without surface modification by cobalt oxide and/or molybdenum oxide and zinc oxide.
The mass percentage content of cobalt oxide and/or molybdenum oxide and zinc oxide on the surface of the catalyst is 0.05-1.5 times higher than that of cobalt oxide and/or molybdenum oxide and zinc oxide in the catalyst.
The alkaline solution comprises: one or more of sodium bicarbonate, ammonium bicarbonate, sodium carbonate, sodium hydroxide and ammonia water. The catalyst calcination temperature is 450-650 ℃.
Preparation of cerium-zirconium solid solution: weighing cerium nitrate and zirconium nitrate according to a stoichiometric ratio, placing the weighed cerium nitrate and zirconium nitrate into a beaker to prepare a mixed solution, adding a pore-expanding agent, dropwise adding ammonia water or a sodium carbonate solution into the mixed solution under the condition of continuously stirring, carrying out coprecipitation reaction, carrying out suction filtration, drying, roasting at 800-950 ℃ for 4-8 hours, and then crushing and grinding into powder. The addition amount of the pore-expanding agent accounts for 1-30% of the mass of the cerium-zirconium solid solution.
The pore-expanding agent is methyl cellulose, active carbon, polyvinyl alcohol, urea or sodium polyacrylate; polyacrylic acid; one or more of ammonium polyacrylate, preferably sodium polyacrylate.
The pore-expanding agent is added into the catalyst step by step, the catalyst has a mesoporous and macroporous structure, and the mass percentage of the pore-expanding agent in the acid solution containing cobalt, molybdenum and zinc is more than 2 times of that in the mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution, so that the penetration sulfur capacity of the adsorption desulfurization catalyst is improved, the olefin saturation rate of the catalyst is low, and the octane number loss is low.
The catalyst contains 25.0-50.0 wt% of zinc oxide, 1.0-15.0 wt% of cobalt oxide and/or molybdenum oxide, 2.0-55.0 wt% of SAPO-11 molecular sieve, 1.0-20.0 wt% of macroporous alumina, 1.0-25.0 wt% of silicon oxide and 1.0-25.0 wt% of cerium-zirconium solid solution, especially the introduction of cerium-zirconium solid solution (a pore-expanding agent is added in the mixing process of the cerium-zirconium solid solution, the ZSM-5 molecular sieve and the macroporous alumina), so that the generation of zinc silicate and zinc aluminate in the high-temperature reduction and regeneration process is effectively inhibited, and the reduction and regeneration stability of the catalyst is improved. The method is suitable for removing sulfur in the catalytically cracked gasoline, the sulfur capacity of the catalyst is reduced by 2-6% after the catalyst is regenerated for 8 times, and the catalyst has good stability.
The present invention will be further illustrated by way of examples to illustrate the measurement method of the present invention, but the present invention is not limited to these examples.
Detailed Description
All starting materials for the present invention are commercially available.
Example 1
Preparation of cerium-zirconium solid solution: weighing 38.8g of cerium nitrate and 33.9g of zirconium nitrate according to a stoichiometric ratio, placing the cerium nitrate and the zirconium nitrate into a beaker to prepare a mixed solution, adding 4g of sodium polyacrylate, dropwise adding ammonia water or a sodium carbonate solution into the mixed solution under the condition of continuous stirring for coprecipitation reaction, then carrying out suction filtration, drying, roasting at 840 ℃ for 6 hours, crushing and grinding into powder.
Preparation of the catalyst: (1) dissolving 70.4g of ammonium molybdate, 149g of zinc nitrate and 15.5g of cobalt nitrate in nitric acid, and adding 22g of sodium polyacrylate to obtain acid liquor containing cobalt, molybdenum and zinc; (2) preparing an acid solution containing 7g of sodium polyacrylate, adding 11g of SAPO-11 molecular sieve, 19g of macroporous alumina and 4.8g of cerium-zirconium solid solution into the acid solution containing sodium polyacrylate, and uniformly stirring to obtain a mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution; and then adding acid liquor containing cobalt salt, molybdenum salt and zinc salt into the mixture slurry, adding sodium carbonate and ammonia water solution, carrying out precipitation reaction, raising the temperature of the obtained reaction product to 90 ℃, aging for 5 hours, filtering, washing, drying and crushing to obtain coprecipitation powder, adding silica sol containing sodium polyacrylate, kneading and molding, and roasting to obtain the finished catalyst. The composition of the catalyst is shown in table 1.
Example 2
The preparation of cerium zirconium solid solution is the same as example 1, the preparation steps of the catalyst are the same as example 1, the mass percentage of the pore-expanding agent in the acid solution containing molybdenum and zinc is higher than that in the mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium zirconium solid solution by 3 times, and the composition of the catalyst is shown in Table 1.
Example 3
The preparation of cerium zirconium solid solution is the same as that of example 1, the preparation steps of the catalyst are the same as that of example 1, and the mass percentage of the pore-expanding agent in the cobalt molybdenum zinc-containing acid solution is 3.5 times higher than that of the pore-expanding agent in the mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium zirconium solid solution in terms of metal oxide. After the catalyst is obtained, cobalt salt, molybdenum salt and zinc salt are prepared and dissolved in dilute nitric acid, the surface of the catalyst is impregnated, and then the catalyst with modified surface is obtained after drying and roasting. The mass percentage content of cobalt oxide, molybdenum oxide and zinc oxide on the surface of the catalyst is 0.8 times higher than that of cobalt oxide, molybdenum oxide and zinc oxide in the catalyst. The composition of the catalyst is shown in table 1.
Example 4
The preparation of the cerium zirconium solid solution is the same as that of example 3, the preparation steps of the catalyst are the same as that of example 3, and the mass percentage content of cobalt oxide, molybdenum oxide and zinc oxide on the surface of the catalyst is 1.4 times higher than that of cobalt oxide, molybdenum oxide and zinc oxide in the catalyst. The composition of the catalyst is shown in table 1.
Table 1 example/comparative catalyst composition/wt%
Comparative example 1
Preparation of the catalyst: (1) dissolving 70.4g of ammonium molybdate, 149g of zinc nitrate and 15.5g of cobalt nitrate in nitric acid, and adding 22g of sodium polyacrylate to obtain acid liquor containing cobalt, molybdenum and zinc; (2) preparing an acid solution containing 7g of sodium polyacrylate, adding 11g of SAPO-11 molecular sieve and 19g of macroporous alumina into the acid solution containing sodium polyacrylate, and uniformly stirring to obtain a mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and a cerium-zirconium solid solution; and adding acid liquor containing cobalt salt, molybdenum salt and zinc salt into the mixture slurry, adding sodium carbonate and ammonia water solution, carrying out precipitation reaction, raising the temperature of the obtained reaction product to 90 ℃, aging for 5 hours, filtering, washing, drying and crushing to obtain coprecipitation powder, adding silica sol containing sodium polyacrylate, kneading, molding and roasting to obtain the comparative catalyst 1.
Comparative example 2
Preparation of cerium-zirconium solid solution: weighing 38.8g of cerium nitrate and 33.9g of zirconium nitrate according to a stoichiometric ratio, placing the cerium nitrate and the zirconium nitrate into a beaker to prepare a mixed solution, adding 4g of sodium polyacrylate, dropwise adding ammonia water or a sodium carbonate solution into the mixed solution under the condition of continuous stirring for coprecipitation reaction, then carrying out suction filtration, drying, roasting at 840 ℃ for 6 hours, crushing and grinding into powder.
Preparation of the catalyst: (1) dissolving 70.4g of ammonium molybdate, 149g of zinc nitrate and 15.5g of cobalt nitrate in nitric acid to obtain acid liquor containing cobalt, molybdenum and zinc; (2) preparing an acid solution, namely adding 11g of SAPO-11 molecular sieve, 19g of macroporous alumina and 4.8g of cerium-zirconium solid solution into the acid solution containing sodium polyacrylate, and uniformly stirring to obtain a mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution; and adding acid liquor containing cobalt salt, molybdenum salt and zinc salt into the mixture slurry, adding 29g of sodium polyacrylate, adding sodium carbonate and an ammonia water solution, carrying out precipitation reaction, raising the temperature of the obtained reaction product to 90 ℃, aging for 5 hours, filtering, washing, drying, crushing to obtain coprecipitation powder, adding silica sol containing sodium polyacrylate, kneading, molding, and roasting to obtain the comparative catalyst 2.
Full-fraction FCC gasoline is adopted to evaluate the adsorption desulfurization catalyst and the comparative catalyst, and the gasoline raw material has olefin content of 32.3 v%, sulfur content of 156ppm and octane number of 89.9.
The evaluation is carried out by adopting a 100ml adiabatic bed, the catalyst or a comparative catalyst is firstly reduced by hydrogen under the pressure of 1.8MPa, the temperature of the bed layer is firstly increased to 360 ℃ and stays for 5 hours, and then the temperature of the bed layer is increased to 460 ℃ and stays for 8 hours to finish the reduction. Catalyst evaluation process conditions: the inlet temperature of the reactor is 320 ℃, the pressure is 1.1MPa, and the space velocity is 5.0h-1The hydrogen-oil volume ratio was 1.0, and the evaluation results are shown in Table 2. The desulfurization rate of the catalyst is more than 89.2 percent, the octane number loss is less than 0.4, the penetrating sulfur capacity is more than 28 percent, and the olefin saturation rate is less than 15 percent. The comparative catalyst 1 has large octane number loss, the comparative catalyst 2 has low desulfurization rate, large octane number loss and low penetrating sulfur capacity. After the adsorbed sulfur capacity reaches saturation, the catalyst or the comparative catalyst is regenerated, and the process conditions are as follows: heating to 260 ℃ at a heating rate of 35 ℃/h in a nitrogen atmosphere, and staying for 7 h; and then regenerating the catalyst, wherein the used regeneration gas is a mixed gas of oxygen and nitrogen, and the volume content of the oxygen accounts for 7 percent of the total gas.
TABLE 2 catalyst and comparative catalyst reaction results
| Desulfurization rate/%) | Loss of octane number | Penetration of sulfur capacity/%) | |
| Example 1 | 90.1 | 0.3 | 30 |
| Example 2 | 89.2 | 0.4 | 28 |
| Example 3 | 91.4 | 0.3 | 29 |
| Example 4 | 91.9 | 0.2 | 32 |
| Comparative example 1 | 89.6 | 1.6 | 28 |
| Comparative example 2 | 86.7 | 1.1 | 18 |
The regenerated catalysts 1 and 4, comparative examples 1 and 2, at a reactor inlet temperature of 320 ℃, a pressure of 1.1MPa and a space velocity of 5.0h-1The evaluation results are shown in Table 3, with a hydrogen-oil volume ratio of 1.0. The desulfurization effect of the catalyst can be basically recovered to the level of a fresh agent, the generation of zinc silicate and zinc aluminate in the high-temperature reduction and regeneration process is effectively inhibited, and the reduction and regeneration stability of the catalyst is improved. Compared with catalysts 1 and 2, the activity is reduced after regeneration, the octane number loss is large, and the penetration sulfur capacity is reduced. After 8 times of regeneration, the desulfurization rate of the catalyst in the embodiment 1 is 85.3 percent, and the sulfur capacity is reduced by 5 percent; example 4 catalyst desulfurization rate 88.4%, reduction of sulfur capacity2％。
TABLE 3 catalyst and comparative catalyst reaction results
| Desulfurization rate/%) | Loss of octane number | Penetration of sulfur capacity/%) | |
| Example 1 | 90.0 | 0.4 | 29 |
| Example 4 | 91.8 | 0.3 | 31 |
| Comparative example 1 | 87.4 | 2.5 | 23 |
| Comparative example 2 | 76.7 | 1.8 | 16 |
Claims (7)
1. An adsorptive desulfurization catalyst, comprising, in weight percent: 25.0-50.0 wt% of zinc oxide, 1.0-15.0 wt% of cobalt oxide and molybdenum oxide, 2.0-55.0 wt% of SAPO-11 molecular sieve, 1.0-20.0 wt% of macroporous alumina, 1.0-25.0 wt% of silicon oxide and 1.0-25.0 wt% of cerium-zirconium solid solution; the mass percentage content of cobalt oxide, molybdenum oxide and zinc oxide on the surface of the catalyst is 0.8-1.5 times higher than that of cobalt oxide, molybdenum oxide and zinc oxide in the catalyst; the preparation method of the catalyst comprises the following steps: (1) dissolving cobalt salt, molybdenum salt and zinc salt in nitric acid, and adding a pore-expanding agent to obtain acid liquor containing cobalt, molybdenum and zinc; (2) preparing an acid solution containing a pore-expanding agent, adding the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution into the acid solution containing the pore-expanding agent, and uniformly stirring to obtain a mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution, wherein the mass percentage of the pore-expanding agent in the acid solution containing cobalt, molybdenum and zinc is more than 2 times that of the pore-expanding agent in the mixture slurry containing the SAPO-11 molecular sieve, the macroporous alumina and the cerium-zirconium solid solution; adding acid liquor containing cobalt salt, molybdenum salt and zinc salt into the mixture slurry, adding alkaline solution, carrying out precipitation reaction, aging the obtained reaction product for 2-5 hours, filtering, washing, drying and crushing to obtain coprecipitation powder, adding a silicon source containing a pore-expanding agent, mixing, kneading, molding and roasting to obtain a catalyst; the catalyst was then further modified: cobalt salt, molybdenum salt and zinc salt are prepared and dissolved in acid, the surface of the catalyst is impregnated, and then the finished product catalyst is obtained after drying and roasting.
2. The adsorptive desulfurization catalyst of claim 1, wherein the catalyst comprises, in weight percent: 25.0-40.0 wt% of zinc oxide, 5.0-15.0 wt% of cobalt oxide and molybdenum oxide, 10.0-50.0 wt% of SAPO-11 molecular sieve, 10.0-20.0 wt% of macroporous alumina, 5.0-25.0 wt% of silicon oxide and 4.0-25.0 wt% of cerium-zirconium solid solution.
3. The adsorptive desulfurization catalyst according to claim 1, wherein the silicon source is one or two of silica gel, sodium silicate, silica micropowder, and diatomaceous earth.
4. The adsorptive desulfurization catalyst of claim 1, wherein the basic solution comprises: one or more of sodium bicarbonate, ammonium bicarbonate, sodium carbonate, sodium hydroxide and ammonia water.
5. The adsorptive desulfurization catalyst according to claim 1, wherein the cerium-zirconium solid solution is prepared as follows: weighing cerium nitrate and zirconium nitrate according to a stoichiometric ratio, placing the cerium nitrate and the zirconium nitrate into a beaker to prepare a mixed solution, adding a pore-expanding agent, dropwise adding ammonia water or a sodium carbonate solution into the mixed solution under the condition of continuously stirring, carrying out coprecipitation reaction, carrying out suction filtration, drying, roasting at 800-950 ℃ for 4-8 h, crushing and grinding into powder, wherein the addition amount of the pore-expanding agent accounts for 1-30% of the mass of the cerium-zirconium solid solution.
6. The adsorption desulfurization catalyst of claim 1, wherein the pore-expanding agent is one or more of methylcellulose, activated carbon, polyvinyl alcohol or urea.
7. The adsorptive desulfurization catalyst according to claim 1, wherein the pore-expanding agent is one or more of sodium polyacrylate, polyacrylic acid and ammonium polyacrylate.
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