CN105833877A - Desulfurization catalyst and preparing method thereof - Google Patents
Desulfurization catalyst and preparing method thereof Download PDFInfo
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- CN105833877A CN105833877A CN201610278788.1A CN201610278788A CN105833877A CN 105833877 A CN105833877 A CN 105833877A CN 201610278788 A CN201610278788 A CN 201610278788A CN 105833877 A CN105833877 A CN 105833877A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 53
- 230000023556 desulfurization Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 54
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 239000011593 sulfur Substances 0.000 claims description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- VSKBCRUQHHGABO-UHFFFAOYSA-N [Al].[H][H].[H][H].[H][H] Chemical compound [Al].[H][H].[H][H].[H][H] VSKBCRUQHHGABO-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B01J35/613—
-
- B01J35/633—
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention provides a desulfurization catalyst and a preparing method thereof .The method includes the steps that after soaked in an active component, a desulfurization catalyst carrier is dried, and the dried catalyst carrier is soaked in an aluminiferous compound solution, dried and roasted to obtain the desulfurization catalyst .The preparing method is easy to operate, the abrasion strength of the catalyst can be improved by 40% or more without affecting reactivity and stability of the catalyst, and fine powder in the use process of the catalyst is effectively reduced .
Description
Technical field
The present invention relates to desulfuration field, specifically, relate to a kind of desulphurization catalyst and preparation method thereof.
Background technology
In the face of increasingly serious environmental problem, the desulfurization that motor petrol carries out the degree of depth is imperative.It is true that it is American-European
The stricter regulation to vehicle gasoline and sulfur content in vehicle gasoline standard formulation in developed country, such as, U.S.'s regulation from
Within 2005, play vehicle gasoline and sulfur content in vehicle gasoline to contain less than 30 μ g/g, regulation merchantable gasoline sulfur from 2009 such as Germany and Japan
Amount not higher than 10 μ g/g.China is the most issued and implements " state V " normal benzine on the ground such as Beijing, Shanghai
Sulfur content reaches 10 below μ g/g, and implements the vapour of " state V " standard from 1 day January in 2018 in China
Oil.This just requires that China must carry out ultra-deep desulfurization to gasoline.China's motor petrol based on catalytically cracked gasoline,
Catalytically cracked gasoline accounts for the ratio of Chinese commodity blended gasoline component and is up to 80%, and the sulfur content in catalytically cracked gasoline is about
Account for the 85%～95% of gasoline total sulfur content.Therefore, the ultra-deep desulfurization to motor petrol to be realized, produce cleaning vapour
Oil, it is important to the ultra-deep desulfurization to catalytically cracked gasoline.
In recent years, hydrogen reaction absorption desulfurization technology is faced owing to having high desulfurization rate, high liquid yield, low hydrogen consumption, little octane
The technical advantages such as value loss and receive much concern, this technology use Ni and Zn be main active component, aluminium oxide and oxidation
Silicon is that the absorbing desulfurization catalyst of main carriers carries out gasoline deep absorption desulfurization under hydro condition.
Face hydrogen reaction process for adsorption desulfuration and can produce the super low-sulfur oil less than 10 μ g/g, and the most successfully realize
Industrialization (improving and development of Zhu Yunxia, Xu Hui .S-Zorb technology. oil Refining Technologies and engineering, 2009,39 (8): 7-12.
Wang Mingzhe, Ruan Yujun. the discussion of adsorbing and desulfurizing catalytic cracking gasoline reaction process condition. oil Refining Technologies and engineering, 2010,
40(9):5-10.).But, as the core of this Technology, the mechanical strength of absorbing desulfurization catalyst is (predominantly
Tear strength) relatively low.Relatively low mechanical strength (mainly tear strength) makes reaction adsorption desulfurizing agent answer in industrialization
Some problems are occurred in that during with.Such as, the serious wear of absorbing desulfurization catalyst, cause the consumption of catalyst
Amount height, adds commercial production cost, also has a certain impact environment.Simultaneously as absorbing desulfurization catalyst
Heavy wear, a large amount of dust that can produce, cause reactor filter easily to block, make blowback cycle time, blowback frequency
Rate increases, so that back-flushing valve serious wear, the lost of life, eventually affects the long period continuous operation of package unit.
(.S-Zorb technology production domesticization in Wu Defei, Zhuan Jian, Yuan Zhongxun, Huang Ze river improves and application. petroleum refining and chemical industry,
2012,43 (7): 76-79)).
The most conventional method is to improve carrier material to improve the mechanical strength of absorbing desulfurization catalyst, such as special in the U.S.
In profit US6271173, US6428685, by the silica portion calcium of one of the support material of absorbing desulfurization catalyst
Compound replace, so that the tear strength of absorbing desulfurization catalyst increases.But, the method uses oxygen
Change calcium the desulphurizing activated of nickel in absorbing desulfurization catalyst is had a significant effect.
Patent CN1422177A is by zinc oxide content and binding agent (mainly Condea in regulation adsorption desulfurizing agent
Company Disperal and the aluminium oxide of Vista Dispal) content, i.e. increasing the consumption of aluminium oxide, to improve absorption de-
The abrasion resistance properties of sulfur catalyst, but the method can reduce the usage amount of active component zinc oxide, thus decrease and urge
The Sulfur capacity of agent.
In patent US 20040048743 and US 20050153838, then to the expanded perlite nitric acid as carrier
Process, thus improve the wear strength of absorbing desulfurization catalyst.But to improving the resistance to of absorbing desulfurization catalyst
Polishing machine limited use.
For the abrasion of absorbing desulfurization catalyst, the reason caused in different types of reactor is variant.Fixing
In bed reactor, the filling process of catalyst can occur the friction between catalyst and between catalyst and wall to damage
Consumption, and in course of reaction, air-flow also can produce abrasion to catalyst to friction and the impact of catalyst surface；?
In fluidized-bed reactor, the friction between catalyst and reacting gas, between agent and agent and between agent and wall is more
Can frequently wear and tear even more serious.
In order to improve the mechanical strength of catalyst, general method is that the appropriate solid added when prepared by catalyst glues
Knot agent makes to be formed between each active component to link, and forms various forms of embedded structure between catalyst components particle
So that the mechanical strength of catalyst, wear strength is made to reach the requirement used.But for absorbing desulfurization catalyst,
In order to ensure desulphurizing activated and sulfur capacity, active component nickel and zinc oxide weight account for the gross weight of catalyst and are up to 70～80
Weight %, the weight of carrier accounts for the gross weight of catalyst and is up to 10～15 weight %, and this makes the consumption of solid binder limit
In the least scope so that the mechanical strength improving absorbing desulfurization catalyst becomes a difficult problem.
Summary of the invention
It is an object of the present invention to provide the preparation method of a kind of desulphurization catalyst.
Another object of the present invention is to the desulphurization catalyst providing described preparation method to prepare.
For reaching above-mentioned purpose, on the one hand, the invention provides the preparation method of a kind of desulphurization catalyst, wherein, described
Method includes, by after the desulphurization catalyst carrier drying of dipping active component, using aluminum contained compound solution to through being dried
Catalyst carrier impregnate, carry out roasting after drying, obtain described desulphurization catalyst.
The present invention is by changing the incorporation way of aluminium oxide, keeping raw catalyst basic structure zinc-aluminium ratio before constant
Put, the wear-resistant index of catalyst can be improved.
The present invention uses aluminum contained compound as mechanical strength supplement, utilizes aluminum contained compound solution to impregnate at catalyst
During can fully, even into catalytic inner, control roasting condition after drying at catalyst and make aluminum contained compound
Fully decomposing, the oxide catalyst filling framing structure after decomposition forms cementation, is fitted together to formation in carrier
Structure is reinforced further, so that absorbing desulfurization catalyst mechanical strength particularly tear strength increases substantially.
According to some specific embodiments of the present invention, wherein, the weight concentration of aluminum contained compound solution is 1-20%.
The present invention is that catalyst carrier is passed through by when preparing prior art conventional desulfurization catalyst according to art methods
After dipping active component, it is dried, does not the most carry out roasting, and with aluminum contained compound solution to dried dipping
The catalyst carrier of active component carries out impregnation process, is then dried, roasting, obtains desulfurization catalyst of the present invention
Agent.
The present invention is defined herein as, and " described desulphurization catalyst " of the present invention refers to according to the inventive method system
The desulphurization catalyst of standby strengthening；And described " conventional desulfurization catalyst " refers to according to common prior art method
The prior art desulphurization catalyst prepared, i.e. without the present invention aluminum contained compound solution impregnation, be dried and roast
The prior art desulphurization catalyst that burning processes.
The preparation method of conventional desulfurization catalyst is well known to those skilled in the art, and e.g., uses active component presoma
Catalyst carrier is impregnated (such as incipient impregnation) by solution, then the catalyst carrier after dipping is dried
And roasting, obtain described conventional desulfurization catalyst.
The present invention can directly by above-mentioned prepare conventional desulfurization catalyst time be used for through the catalyst carrier of impregnation drying
The present invention, and without additionally carrying out any changing to by the process of active component precursor solution impregnated catalyst support
Enter.
Conventional desulfurization catalyst of the present invention can be desulphurization catalyst commonly used in the art, and according to this
Brighter specific embodiments, wherein, described desulphurization catalyst be active component be the desulphurization catalyst of Ni and Zn.
The precursor salt of described active component can be that prior art is conventional use of, and such as the precursor salt of Ni is permissible
For nickel nitrate, nickelous carbonate, nickel sulfate and nickel hydroxide etc.；The precursor salt of Zn can be zinc oxide, meta-sodium zincate,
With zinc sulfate etc..
It should be appreciated that active component described here refers to the element itself existed as active component；But it is actual
Upper described active component is generally presented in its oxide.This point is well known to those skilled in the art.
According to some specific embodiments of the present invention, wherein, the mol ratio of Ni and Zn is 0.2-0.8.
Described catalyst carrier is conventional desulfurization catalyst carrier, and those skilled in the art generally know and are adapted as
The raw material of desulfurization catalyst agent carrier, and according to some specific embodiments of the present invention, wherein, described catalyst carrier is extremely
Contain the mixing of one or more in aluminium oxide, silicon oxide, titanium dioxide and zirconium oxide less；
According to some specific embodiments of the present invention, wherein, described catalyst carrier at least contains aluminium oxide and silicon oxide.
According to some specific embodiments of the present invention, wherein, the weight ratio of aluminium oxide and silicon oxide is 1.0-1.5.
According to some specific embodiments of the present invention, wherein, described catalyst carrier is possibly together with molecular sieve or montmorillonite.
According to some specific embodiments of the present invention, wherein, described molecular sieve divides selected from ZSM-5 molecular sieve or layer post
Son sieve.
According to some specific embodiments of the present invention, wherein, the weight of molecular sieve or montmorillonite and aluminium oxide and silicon oxide
Gross weight than for 1:6-1:15.
According to some specific embodiments of the present invention, wherein, the weight of molecular sieve or montmorillonite and aluminium oxide and silicon oxide
Gross weight than for 4:25 and 2:25.
According to some specific embodiments of the present invention, wherein, described aluminum contained compound is selected from aluminium hydroxide, biphosphate
One or more in aluminum, aluminum nitrate, aluminum chloride, aluminum sulfate and complex aluminate.
According to some specific embodiments of the present invention, wherein, be preferably selected from aluminium hydroxide, aluminium dihydrogen phosphate, aluminum nitrate,
In aluminum chloride, aluminum sulfate and complex aluminate two kinds.
Described complex aluminate such as can be able to be aluminum chloride complexation for the conventional use of complex aluminate in this area
Thing, alumine hydroxide colloid etc..
According to some specific embodiments of the present invention, wherein, more preferably when selected from two kinds, two kinds of aluminum contained compound weights
Amount ratio is 1:1.
According to some specific embodiments of the present invention, wherein, active component is 2:1-5:1 with the weight ratio of carrier；
According to some specific embodiments of the present invention, wherein, active component is 3:1 with the weight ratio of carrier.
According to some specific embodiments of the present invention, wherein, aluminum contained compound consumption is for making aluminum contained compound after roasting
Residue butt is the 1-6% of total catalyst weight.
According to some specific embodiments of the present invention, wherein, described aluminum contained compound solution ph is 2-9；
According to some specific embodiments of the present invention, wherein, the most described aluminum contained compound solution is to regulate with ammonia
PH value is to 2-9.
According to some specific embodiments of the present invention, wherein, use aluminum contained compound solution to the catalyst through being dried
When carrier impregnates, solid-to-liquid ratio is 0.2-1.5.
According to some specific embodiments of the present invention, wherein, it is roasted to roasting at 450-600 DEG C described in；
According to some specific embodiments of the present invention, wherein, preferably roasting 0.5-4h.
On the other hand, present invention also offers the desulphurization catalyst that described preparation method prepares.
According to some specific embodiments of the present invention, wherein, described desulphurization catalyst Sulfur capacity in use is maintained at
10-19%.
According to some specific embodiments of the present invention, wherein, described desulphurization catalyst pore volume is 0.25-0.35cm3/ g,
Specific surface area is 25-45m2/g。
In sum, the invention provides a kind of desulphurization catalyst and preparation method thereof.The desulphurization catalyst tool of the present invention
Have the following advantages:
The present invention has easy and simple to handle, the tear strength of catalyst can be improved more than 40%, not affect catalyst
Reactivity, stability, effectively reduce the generation of fine powder during catalyst uses；The catalyst pore volume made is protected
Holding at 0.25～0.35 ml/g, specific surface area is maintained at 25～45 meters squared per gram.Sulfur during catalyst uses
Hold and be maintained at 3～11%, the sulfur content in gasoline can be dropped to 10 below μ g/g, directly meet following state V class gasoline
Discharge standard, have simultaneously octane number loss low (RON loss < 0.5～1.0), Volume Loss few (< 1.0v%),
The plurality of advantages such as hydrogen consumes less, hydrogen purity is less demanding.
Detailed description of the invention
Implementation process and the beneficial effect of generation of the present invention is described in detail, it is intended to help to read below by way of specific embodiment
Reader is more fully understood that essence and the feature of the present invention, not as can the restriction of practical range to this case.
In embodiments, catalyst abrasion index presses ASTM D5757-2000 standard test, BET specific surface and
Pore volume uses GB/T5816-1995 method to measure；Composition assay use x-ray fluorescence analyzer according to
GB/T12690.5-90 measures；Hydrogen sulfide adsorption Sulfur capacity measures and carries out by chemical industry standard HG/T2513-93 method.
Other detection sees (" oil and oil product test method national standard " published by China Standards Press 1989).
Embodiment 1
Adding the deionized water dissolving preparation phosphate dihydrogen aluminum solution containing 10 weight % with aluminium dihydrogen phosphate, use ammonia will
It is standby that solution ph is adjusted to 7-9.Take the absorbing desulfurization catalyst after 100g impregnation drying, consisting of of this catalyst
Nickel oxide 23 weight %, zinc oxide 48 weight %, aluminium oxide 13 weight %, silicon oxide 12 weight %, cover torr soil 4 weight %.
Being mixed with phosphate dihydrogen aluminum solution by 100g absorbing desulfurization catalyst, liquid-solid ratio is 0.8, then under the conditions of 200 DEG C
It is dried 1 hour, then roasting 1 hour at 500 DEG C in muffle furnace, with deionised water, dry after cooling
Dry, it is prepared as the catalyst of embodiment 1.
Embodiment 2
Add the deionized water dissolving preparation aluminum nitrate solution containing 15 weight % with aluminum nitrate, use ammonia by solution ph
It is adjusted to 4.0 standby.Take the absorbing desulfurization catalyst after 100g impregnation drying, this catalyst consist of nickel oxide 23
Weight %, zinc oxide 48 weight %, aluminium oxide 13 weight %, silicon oxide 12 weight %, ZSM-5 shape-selective molecular sieve 4 weight %.
Being mixed with aluminum nitrate solution by 100g absorbing desulfurization catalyst, liquid-solid ratio is 0.8, then carries out under the conditions of 200 DEG C
Being dried 1 hour, then roasting 1 hour at 500 DEG C in muffle furnace, is prepared as the catalyst of embodiment 2.
Embodiment 3
Add the deionized water dissolving preparation liquor alumini chloridi containing 12 weight % with aluminum chloride, use ammonia by solution ph
It is adjusted to 6.0 standby.Take the absorbing desulfurization catalyst after 100g impregnation drying, this catalyst consist of nickel oxide 23
Weight %, zinc oxide 48 weight %, aluminium oxide 13 weight %, silicon oxide 12 weight %, layered molecular sieve 4 weight %.By 100g
Absorbing desulfurization catalyst mixes with aluminum hydroxide solution, and liquid-solid ratio is 0.8, is then dried 1 under the conditions of 200 DEG C
Hour, then roasting 1 hour at 500 DEG C in muffle furnace, is prepared as the catalyst of embodiment 3.
Embodiment 4
Add the deionized water dissolving preparation liquor alumini chloridi containing 12 weight % with aluminum chloride, use ammonia by solution ph
It is adjusted to 6.0 standby.Take the absorbing desulfurization catalyst after 100g impregnation drying, this catalyst consist of nickel oxide 25
Weight %, zinc oxide 50 weight %, aluminium oxide 14 weight %, silicon oxide 11 weight %.By 100g absorbing desulfurization catalyst with
Aluminum hydroxide solution mixes, and liquid-solid ratio is 0.8, is then dried under the conditions of 200 DEG C 1 hour, then horse
In good fortune stove, roasting 1 hour at 500 DEG C, is prepared as the catalyst of embodiment 4.
Embodiment 5
Adding the deionized water dissolving preparation phosphate dihydrogen aluminum solution containing 10 weight % with aluminium dihydrogen phosphate, use ammonia will
It is standby that solution ph is adjusted to 7-9.Take the absorbing desulfurization catalyst after 100g impregnation drying, consisting of of this catalyst
Nickel oxide 23 weight %, zinc oxide 48 weight %, aluminium oxide 15 weight %, silicon oxide 10 weight %, cover torr soil 2 weight %.
Being mixed with phosphate dihydrogen aluminum solution by 100g absorbing desulfurization catalyst, liquid-solid ratio is 0.8, then under the conditions of 200 DEG C
It is dried 1 hour, then roasting 1 hour at 500 DEG C in muffle furnace, with deionised water, dry after cooling
Dry, it is prepared as the catalyst of embodiment 5.
Embodiment 6
Add the deionized water dissolving preparation aluminum nitrate solution containing 15 weight % with aluminum nitrate, use ammonia by solution ph
It is adjusted to 4.0 standby.Take the absorbing desulfurization catalyst after 100g impregnation drying, this catalyst consist of nickel oxide 14
Weight %, zinc oxide 58 weight %, aluminium oxide 12 weight %, silicon oxide 12 weight %, ZSM-5 shape-selective molecular sieve 2 weight %.
Being mixed with aluminum nitrate solution by 100g absorbing desulfurization catalyst, liquid-solid ratio is 0.8, then carries out under the conditions of 200 DEG C
Being dried 1 hour, then roasting 1 hour at 500 DEG C in muffle furnace, is prepared as the catalyst of embodiment 6.
Comparative example 1
Select South Chemical Company of Germany to produce and face the absorption desulfurization used on hydrogen adsorption desulfurization commercial plant at gasoline
Catalyst is contrast medium.
Test case 1
Obtain mechanical strength data by the abrasion index comparing absorbing desulfurization catalyst, by contrast physical parameter, wear
Sulfur capacity and single hop response time illustrate the implementation result of the present invention and provide one not have catalyst serviceability thoroughly
The mechanical strength of impact improves method.
The abrasion index transitivity parameter of table 1 embodiment 1-6 and comparative example 1
Table 1 is abrasion index and the catalyst structure supplemental characteristic using this method rear catalyst, shows the machine of catalyst
Tool intensity is greatly improved and physical arrangement parameter does not has significant change.
In order to verify the serviceability of catalyst further, using Industrial Catalysis cracking gasoline is raw material, is shown in Table 2.
Table 2 raw oil character
Table 3 embodiment 1-6 and the working sulfur capacity of comparative example 1 and single hop response time
The composition contrast of table 4 adsorption reaction product race
| Project | Saturated hydrocarbons, v% | Alkene, v% | Aromatic hydrocarbons, v% | Olefin loss, v% | △RON |
| Embodiment 1 | 50.18 | 32.22 | 17.60 | 4.30 | 0.8 |
| Comparative example 1 | 51.42 | 31.19 | 17.38 | 5.33 | 1.0 |
| Embodiment 2 | 50.71 | 33.21 | 16.08 | 3.31 | 0.7 |
| Embodiment 3 | 49.98 | 32.89 | 17.13 | 3.63 | 0.7 |
| Embodiment 4 | 50.13 | 32.41 | 17.46 | 4.11 | 0.8 |
| Embodiment 5 | 52.01 | 33.54 | 14.45 | 2.98 | 0.6 |
| Embodiment 6 | 50.28 | 32.21 | 17.51 | 4.31 | 0.8 |
Catalyst pre-reduction to nickel is zero-valent state.Reaction be 420 DEG C, hydrogen pressure 2.5Mpa, hydrogen/oil mole
When ratio 0.3 and weight space velocity 6 are little-1The working sulfur capacity of lower mensuration absorbing desulfurization catalyst, single hop response time and liquid are received
Situation, table 3.
Wherein penetrate and refer to that working sulfur capacity refers to wear from absorption starts to break through 10ug/g to outlet content of sulfur in gasoline
A co-adsorption sulfur content on adsorbent before thoroughly, the single hop response time then refers to the response time before penetrating, can be to regeneration
Cycle has a direct impact.
Embodiment 1 that what table 4 was given is and comparative example 1 adsorption reaction product race form when loss of octane number situation,
The effect of the present invention is all better than the implementation result of comparative example.
Process conditions when table 5 then gives recycling and effect.
Process conditions when table 5 recycles and Contrast on effect
| Project | Burn temperature | Burn O2 | Reduction temperature | Reduction H2 | S in product | Stablize Sulfur capacity |
| Embodiment 1 | 520℃ | Air | 420℃ | 2.6Mpa | 10ug/g | 5.2 weight % |
| Comparative example 1 | 520℃ | Air | 420℃ | 2.6Mpa | 10ug/g | 3.8 weight % |
| Embodiment 2 | 520℃ | Air | 420℃ | 2.6Mpa | 10ug/g | 5.5 weight % |
| Embodiment 3 | 520℃ | Air | 420℃ | 2.6Mpa | 10ug/g | 4.9 weight % |
| Embodiment 4 | 520℃ | Air | 420℃ | 2.6Mpa | 10ug/g | 5.6 weight % |
| Embodiment 5 | 520℃ | Air | 420℃ | 2.6Mpa | 10ug/g | 5.1 weight % |
| Embodiment 6 | 520℃ | Air | 420℃ | 2.6Mpa | 10ug/g | 4.5 weight % |
Claims (10)
1. a preparation method for desulphurization catalyst, wherein, described method includes urging the desulfurization of dipping active component
After agent carrier drying, use aluminum contained compound solution that the catalyst carrier through being dried is impregnated, be dried laggard
Row roasting, obtains described desulphurization catalyst；The preferably weight concentration of aluminum contained compound solution is 1-20%.
Preparation method the most according to claim 1, wherein, described active component is Ni and Zn；Preferably Ni
It is 0.2-0.8 with the mol ratio of Zn.
Preparation method the most according to claim 1, wherein, described catalyst carrier at least contain aluminium oxide,
The mixing of one or more in silicon oxide, titanium dioxide and zirconium oxide；Preferably at least contain aluminium oxide and silicon oxide
Combination；Wherein the weight ratio of preferential oxidation aluminum and silicon oxide is 1.0-1.5；The most described catalyst carrier is possibly together with molecule
Sieve or montmorillonite；The most preferred described molecular sieve is selected from ZSM-5 molecular sieve or layered molecular sieve；Preferred molecular sieve or
The gross weight of the weight of montmorillonite and aluminium oxide and silicon oxide is than for 1:6-1:15.
Preparation method the most according to claim 1, wherein, described aluminum contained compound is selected from aluminium hydroxide, phosphorus
One or more in acid dihydride aluminum, aluminum nitrate, aluminum chloride, aluminum sulfate and complex aluminate；Be preferably selected from aluminium hydroxide,
In aluminium dihydrogen phosphate, aluminum nitrate, aluminum chloride, aluminum sulfate and complex aluminate two kinds；More preferably when selected from two kinds,
Two kinds of aluminum contained compound weight ratios are 0.1-1.0:1, most preferably 1:1.
Preparation method the most according to claim 1, wherein, active component is 2:1-5 with the weight ratio of carrier:
1；It is preferably 3:1.
Preparation method the most according to claim 1, wherein, aluminum contained compound consumption is for containing aluminum after making roasting
Compound residue butt is the 1-6% of total catalyst weight.
Preparation method the most according to claim 1, wherein, described aluminum contained compound solution ph is 2-9；
The most described aluminum contained compound solution is with ammonia regulation pH value to 2-9.
Preparation method the most according to claim 1, wherein, uses aluminum contained compound solution to be dried process
When catalyst carrier impregnates, solid-to-liquid ratio is 0.2-1.5.
Preparation method the most according to claim 1, wherein, described in be roasted to roasting at 450-600 DEG C；Excellent
Select roasting 0.5-4h.
10. the desulphurization catalyst that the preparation method described in claim 1～9 any one prepares；The most described de-
Sulfur catalyst Sulfur capacity in use is maintained at 10-19%；It is also preferred that desulphurization catalyst pore volume is
0.25-0.35cm3/ g, specific surface area is 25-45m2/g。
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| CN109364971A (en) * | 2018-10-22 | 2019-02-22 | 新疆环境工程技术有限责任公司 | Desulphurization catalyst and preparation method thereof |
| CN112604651A (en) * | 2020-12-18 | 2021-04-06 | 湖北润驰环保科技有限公司 | Method for preparing high-efficiency desulfurizer by using waste molecular sieve catalyst and waste zinc oxide desulfurizer as raw materials |
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| CN112604651A (en) * | 2020-12-18 | 2021-04-06 | 湖北润驰环保科技有限公司 | Method for preparing high-efficiency desulfurizer by using waste molecular sieve catalyst and waste zinc oxide desulfurizer as raw materials |
| CN112604651B (en) * | 2020-12-18 | 2023-06-09 | 湖北润驰环保科技有限公司 | Method for preparing efficient desulfurizing agent by using waste molecular sieve catalyst and waste zinc oxide desulfurizing agent as raw materials |
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