CN113441124A - Carbonyl sulfide hydrolysis catalyst and preparation method thereof - Google Patents
Carbonyl sulfide hydrolysis catalyst and preparation method thereof Download PDFInfo
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- CN113441124A CN113441124A CN202110719490.0A CN202110719490A CN113441124A CN 113441124 A CN113441124 A CN 113441124A CN 202110719490 A CN202110719490 A CN 202110719490A CN 113441124 A CN113441124 A CN 113441124A
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- carbonyl sulfide
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 68
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 15
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 15
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 15
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 22
- 150000004645 aluminates Chemical class 0.000 claims description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 11
- 230000008021 deposition Effects 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 26
- 239000011148 porous material Substances 0.000 description 14
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000019086 sulfide ion homeostasis Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- -1 vanadium metal oxide Chemical class 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a carbonyl sulfide hydrolysis catalyst and a preparation method thereof. The carbonyl sulfide hydrolysis catalyst is prepared from the following raw materials: gamma-Al2O360-85 parts by weight; 1-5 parts by weight of a titanium-containing material; the weight of the potassium oxide precursor is 3-20Weighing parts; 1-10 parts by weight of polyvinyl alcohol; 0.3-5 parts by weight of carboxymethyl cellulose; 2-10 parts by weight of ammonium bicarbonate; 3-15 parts of a binder. The carbonyl sulfide hydrolysis catalyst has high carbonyl sulfide hydrolysis rate at low temperature, and can reduce the occurrence of sulfur deposition.
Description
Technical Field
The invention relates to a carbonyl sulfide hydrolysis catalyst and a preparation method thereof.
Background
Blast furnace gas is used as combustible gas with the largest output in iron and steel enterprises, is sent to user units such as a blast furnace hot blast stove, a steel rolling heating furnace, gas power generation and the like after being subjected to residual pressure power generation and is used as fuel, but the blast furnace gas still contains more organic sulfur harmful impurities. The main component of organic sulfur is carbonyl sulfide. The carbonyl sulfide has relatively stable physicochemical properties, low acidity, polarity and chemical activity and is difficult to remove. The currently common methods for removing carbonyl sulfide are mainly divided into wet method and dry method desulfurization. The wet desulfurization mainly comprises a liquid phase catalytic hydrolysis method and an organic amine solution absorption method. The wet desulphurization has the defects of difficult waste liquid discharge treatment, high solvent regeneration energy consumption, low desulphurization precision and the like. The dry desulfurization mainly comprises an adsorption method, a catalytic hydrolysis method and a hydrogenation conversion method. The desulfurization precision of the dry desulfurization is high, no waste slag and liquid are discharged, and the process is simple. Therefore, dry removal of carbonyl sulfide is currently the main research direction. The hydrolysis method has the advantages of mild reaction conditions, no consumption of raw material gas, less side reactions, relatively low energy consumption and the like, and is developed rapidly in recent years.
CN101108339A discloses a preparation method of a medium-temperature carbonyl sulfide hydrolysis catalyst. Uniformly mixing a precursor pseudo-boehmite of a carrier alumina-based component, a precursor potassium carbonate of an active promoter alkali metal oxide-based component, a precursor vanadium pentoxide of a modifier vanadium metal oxide-based component and a pore-forming agent, adding the mixture for bonding, extruding the mixture at normal temperature for molding, standing the mixture at normal temperature for 12 to 24 hours, drying the mixture at 100 to 150 ℃ for 2 to 4 hours, and finally roasting the dried mixture at 500 to 700 ℃ for 2 to 4 hours to obtain a finished catalyst; the pore-forming agent is a mixture of three pore-forming agents of cellulose, polymer and inorganic matter, and the binder is water or nitric acid. The hydrolysis catalyst is a medium-temperature catalyst, and the applicable temperature is 200-400 ℃.
CN106861665B discloses a preparation method of an alumina carbonyl sulfide hydrolysis catalyst: providing soluble aluminum salt, polystyrene microspheres, a mesoporous template agent P123, potassium oxalate, oxalic acid, ethylene glycol, methanol, absolute ethyl alcohol, fatty alcohol-polyoxyethylene ether and distilled water; preparing a solution of an alumina precursor, a solution of a mesoporous template, a polystyrene microsphere macroporous template and a potassium oxalate coordination solution of an active component precursor; mixing the solution of the alumina precursor and the solution of the mesoporous template to obtain a mixed solution; immersing the polystyrene microsphere macroporous template into the mixed solution and filling the mixed solution into the polystyrene microsphere macroporous template to obtain a primary composite; spraying the active component precursor potassium oxalate coordination solution into the primary composite and allowing the active component precursor potassium oxalate coordination solution to permeate into the primary composite to obtain a secondary composite; and roasting the secondary complex by a two-stage temperature programming roasting method to obtain the alumina carbonyl sulfide hydrolysis catalyst with the step holes. The catalyst has low conversion rate and short duration of carbonyl sulfide.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a carbonyl sulfide hydrolysis catalyst which has a high carbonyl sulfide hydrolysis rate at low temperatures and can reduce the occurrence of a sulfur deposition phenomenon. Another object of the present invention is to provide a method for preparing a carbonyl sulfide hydrolysis catalyst.
The technical purpose is achieved through the following technical scheme.
In one aspect, the invention provides a carbonyl sulfide hydrolysis catalyst prepared from raw materials comprising:
wherein, the gamma-Al2O3The preparation method comprises the following steps:
(a) gelatinizing an aluminate solution at the temperature of 50-75 ℃ and the pH of 9.5-12 to form pseudo-boehmite;
(b) aging pseudo-boehmite at the temperature of 80-105 ℃ and the pH value of 10-12.5 to obtain a crystal;
(c) washing the crystal, and drying at 80-120 ℃ to obtain a precursor;
(d) roasting the precursor at 350-650 ℃ to obtain gamma-Al2O3。
According to the carbonyl sulfide hydrolysis catalyst, the weight ratio of the polyvinyl alcohol to the carboxymethyl cellulose to the ammonium bicarbonate is preferably (3-6) to 2 (4-7).
According to the carbonyl sulfide hydrolysis catalyst, preferably, the potassium oxide precursor is potassium carbonate, and the titanium-containing material is titanium dioxide.
According to the carbonyl sulfide hydrolysis catalyst, preferably, the concentration of the aluminate solution is 0.5-2 mol/L calculated by alumina;
reacting an aluminate solution with an acidic substance to form a pseudoboehmite; wherein the acidic substance is selected from sulfuric acid solution or acidic liquid formed by introducing carbon dioxide into water.
According to the carbonyl sulfide hydrolysis catalyst, the aging time is preferably 2-8 hours, the drying time is preferably 2-9 hours, and the roasting time is preferably 2-8 hours.
According to the carbonyl sulfide hydrolysis catalyst of the invention, preferably, the binder is selected from one or more of sesbania powder, citric acid, nitric acid, acetic acid or water.
According to the carbonyl sulfide hydrolysis catalyst of the present invention, preferably, the aluminate in the aluminate solution is selected from one or more of sodium aluminate or potassium aluminate.
On the other hand, the invention also provides a preparation method of the carbonyl sulfide hydrolysis catalyst, which comprises the following steps:
(1) will comprise gamma-Al2O3Mixing the raw materials of titanium-containing substance, potassium oxide precursor, polyvinyl alcohol, carboxymethyl cellulose, ammonium bicarbonate and binder, and molding to obtain a blank;
(2) drying the green body by adopting a hot air method to obtain a dried green body;
(3) roasting the dried green body: heating to 400-500 ℃ at a heating rate of 3-10 ℃/min, and roasting at a constant temperature for 1-5 h; then heating to 500-650 ℃ at the heating rate of 5-13 ℃/min, and roasting at constant temperature for 1-5 h; cooling to obtain the carbonyl sulfide hydrolysis catalyst.
According to the preparation method provided by the invention, the drying temperature is preferably 80-120 ℃.
The preparation method according to the invention preferably further comprises preparing gamma-Al2O3The steps of (1):
(a) gelatinizing an aluminate solution at the temperature of 50-75 ℃ and the pH of 9.5-12 to form pseudo-boehmite;
(b) aging pseudo-boehmite at the temperature of 80-105 ℃ and the pH value of 10-12.5 to obtain a crystal;
(c) washing the crystal, and drying at 80-120 ℃ to obtain a precursor;
(d) roasting the precursor at 350-650 ℃ to obtain gamma-Al2O3。
The invention prepares the gamma-Al by a specific method2O3Has abundant pores; under the action of polyvinyl alcohol, carboxymethyl cellulose and ammonium bicarbonate in certain proportion2O3Form macropores and mesopores in the pore structure of (A) and form micropores on the pore channel, which is helpful for hydrolysis of carbonyl sulfide and H2S is diffused, so that sulfur deposition is reduced; titanium dioxide and potassium carbonate can further improve the pore structure, contribute to carbonyl sulfide hydrolysis and H2And (4) S is diffused.
Detailed Description
The present invention is described in more detail below, but the present invention is not limited thereto.
< carbonyl sulfide hydrolysis catalyst >
The carbonyl sulfide hydrolysis catalyst is a low-temperature carbonyl sulfide hydrolysis catalyst, and the temperature of the carbonyl sulfide hydrolysis catalyst is 30-100 ℃; preferably 50-100 ℃; preferably 60 to 90 ℃.
The carbonyl sulfide hydrolysis catalyst is prepared from the following raw materials: gamma-Al2O3The composite material comprises titanium-containing substances, a potassium oxide precursor, polyvinyl alcohol, carboxymethyl cellulose, ammonium bicarbonate and a binder. Root of herbaceous plantAccording to one embodiment of the invention, the starting material consists of gamma-Al2O3Titanium dioxide, potassium carbonate, polyvinyl alcohol, carboxymethyl cellulose, ammonium bicarbonate and a binder.
Gamma-Al of the invention2O3The preparation method comprises the following steps: (a) gelling; (b) aging; (c) washing and drying; (d) and (5) roasting.
In the step (a), the aluminate solution is gelatinized at the temperature of 50-75 ℃ and the pH of 9.5-12 to form the pseudoboehmite. Specifically, an aluminate solution is reacted with an acidic material to form a pseudoboehmite. The acidic substance is selected from sulfuric acid solution or acidic liquid formed by introducing carbon dioxide into water. H in sulfuric acid solution+The concentration of (A) is 0.3-1 mol/L; preferably 0.3-0.8 mol/L; more preferably 0.4 to 0.7 mol/L. The pseudo-boehmite prepared by the method has high purity, can obtain a precursor with a developed pore structure, and is beneficial to improving the hydrolysis rate of carbonyl sulfide and reducing sulfur deposition.
The aluminate in the aluminate solution may be selected from one or more of sodium aluminate or potassium aluminate. According to one embodiment of the invention, the aluminate in the aluminate solution is sodium aluminate. The concentration of the aluminate solution is 0.5-2 mol/L calculated by alumina; preferably 0.8-1.5 mol/L; more preferably 1.1 to 1.3 mol/L. The gelling temperature is 50-75 ℃; preferably 55-70 ℃; more preferably 55 to 65 ℃. The pH value of the gel is 9.5-12; preferably 9.5 to 11; more preferably 9.8 to 10.5. The pseudo-boehmite prepared by the method has high purity, can obtain a precursor with a developed pore structure, and is beneficial to improving the hydrolysis rate of carbonyl sulfide and reducing sulfur deposition.
In the step (b), the pseudoboehmite is aged at the temperature of 80-105 ℃ and the pH value of 10-12.5 to obtain a crystal. Thus, the loose flocculent gel generated in the gelling process can be further crystallized to generate crystal grains, the crystallinity is improved, and the formation of the gamma-Al with developed pore structure is facilitated2O3The method is favorable for improving the hydrolysis rate of carbonyl sulfide and reducing sulfur deposition.
The aging temperature is 80-105 ℃; preferably 85-100 ℃; more preferably 85 ^ e95 ℃. The aging pH is 10-12.5; preferably 10 to 11.5; more preferably 10 to 10.5. Thus, gamma-Al contributing to development of pore structure2O3Is performed.
In the step (c), the crystal is washed and then dried at 80-120 ℃ to obtain a precursor. The crystals may be washed with dilute nitric acid. Drying may be carried out in an oven. The drying temperature can be 80-120 ℃; preferably 90-110 ℃; more preferably 100 to 110 ℃. The drying time can be 2-9 h; preferably 2-6 h; more preferably 3 to 5 hours. This helps to maintain the pore structure.
In the step (d), the precursor is roasted at 350-650 ℃ to obtain gamma-Al2O3. The roasting temperature is 350-650 ℃; preferably 400-600 ℃; more preferably 520 to 600 ℃. The roasting time can be 2-8 h; preferably 3-6 h; more preferably 3 to 5 hours. This contributes to the production of gamma-Al having a developed pore structure2O3。
In the present invention, gamma-Al2O3The amount of the (B) is 60-85 parts by weight; preferably 65 to 80 parts by weight; more preferably 68 to 70 parts by weight. This helps to obtain a high carbonyl sulfide hydrolysis content and H2S is a hydrolysis catalyst which diffuses rapidly.
The amount of the titanium-containing material can be 1-5 parts by weight; preferably 1 to 4 parts by weight; more preferably 1 to 3 parts by weight. The amount of the potassium oxide precursor can be 3-20 parts by weight; preferably 5 to 15 parts by weight; more preferably 10 to 12 parts by weight. The titanium-containing material may be a titanium-containing compound or a titanium-containing salt. The titanium-containing compound is preferably titanium dioxide. The precursor of potassium oxide may be potassium carbonate. The titanium and the potassium are matched with each other, so that the hydrolysis performance of the catalyst on COS can be improved, the sulfur poisoning resistance of the catalyst can be enhanced, and H is improved2S diffusion rate, reducing sulfur deposition.
The polyvinyl alcohol can be used in an amount of 1 to 10 parts by weight; preferably 2 to 6 parts by weight; more preferably 4 to 5 parts by weight. The amount of the carboxymethyl cellulose is 0.3-5 parts by weight; preferably 1 to 4 parts by weight; more preferably 1 to 3 parts by weight. The amount of ammonium bicarbonate can be 2-10 parts by weight; preferably 4 to 8 parts by weight; more preferably 4 to 6 parts by weight. Therefore, the pore structure of the carbonyl sulfide hydrolysis catalyst can be improved, the hydrolysis rate of carbonyl sulfide can be improved, and the sulfur deposition can be reduced.
In the invention, the weight ratio of the polyvinyl alcohol to the carboxymethyl cellulose to the ammonium bicarbonate can be (3-6) to (2) - (4-7); preferably, the weight ratio of the polyvinyl alcohol to the carboxymethyl cellulose to the ammonium bicarbonate is (3-5) to 2 (4-6); more preferably, the weight ratio of polyvinyl alcohol, carboxymethyl cellulose and ammonium bicarbonate is 4:2: 5. This enables the gamma-Al in the present invention2O3Has a more suitable pore structure, is beneficial to the rapid diffusion of hydrogen sulfide and reduces the sulfur deposition.
The binder may be selected from one or more of sesbania powder, citric acid, nitric acid, acetic acid or water. Preferably, the binder is selected from one or more of nitric acid, acetic acid or water. More preferably, the binder is acetic acid and water. The amount of the binder can be 3-15 parts by weight; preferably 5 to 10 parts by weight; more preferably 6 to 7 parts by weight. The excessive consumption of the binder is not beneficial to the formation of a pore structure; if the amount is too small, the molding of the carbonyl sulfide hydrolysis catalyst is not favorable.
< preparation of catalyst for hydrolyzing carbonyl sulfide >
The preparation method of the carbonyl sulfide hydrolysis catalyst comprises the following steps: (1) a step of molding; (2) a step of drying; and (3) a step of baking.
In the step (1), gamma-Al is included2O3The raw materials of titanium-containing material, potassium oxide precursor, polyvinyl alcohol, carboxymethyl cellulose, ammonium bicarbonate and binder are mixed and molded to obtain a blank. In certain embodiments, the feedstock is formed from gamma-Al2O3The composite material comprises titanium-containing substances, a potassium oxide precursor, polyvinyl alcohol, carboxymethyl cellulose, ammonium bicarbonate and a binder. The composition and amounts of the starting materials are as specified above. The forming mode can adopt one of a rotating balling method, a kneading and extruding method and a honeycomb forming method; preferably, it is one selected from a rolling ball method or a kneading bar extrusion method.
And (2) drying the blank by adopting a hot air method to obtain a dried blank. The drying temperature can be 80-120 ℃; preferably 90-110 ℃; more preferably 95 to 105 ℃.
In the step (3), roasting the dried green body: heating to a first roasting temperature at a first heating speed, and roasting at the constant temperature at the first roasting temperature; then heating to a second roasting temperature at a second heating speed, and roasting at the constant temperature at the second roasting temperature; cooling to obtain the carbonyl sulfide hydrolysis catalyst. The first temperature rise speed is 3-10 ℃/min; preferably 4-8 ℃/min; more preferably 5 to 7 ℃/min. The first roasting temperature is 400-500 ℃; preferably 400-480 ℃; more preferably 400 to 450 ℃. According to one embodiment of the present invention, the first firing temperature is 400 to 430 ℃. The constant-temperature roasting time at the first roasting temperature can be 1-5 h; preferably 1-4 h; more preferably 1 to 3 hours. The second temperature rise speed is 5-13 ℃/min; preferably 6-10 ℃/min; more preferably 7 to 9 ℃/min. The second roasting temperature is 500-650 ℃; preferably 500-600 ℃; more preferably 520 to 580 ℃. The constant-temperature roasting time at the second roasting temperature can be 1-5 h; preferably 1-4 h; more preferably 1 to 3 hours. Such calcination step and calcination conditions facilitate the formation of a pore structure in the carbonyl sulfide hydrolysis catalyst, increase the hydrolysis rate of the catalyst for carbonyl sulfide, and facilitate rapid diffusion of hydrogen disulfide.
Preparation example 1
(a) Mixing sodium aluminate solution with sulfuric acid solution (H)+Concentration of 0.6mol/L) and fully contacting to form gel to obtain pseudoboehmite;
(b) aging the pseudoboehmite to obtain a crystal;
(c) washing the crystal with dilute nitric acid, and drying in an oven to obtain a precursor;
(d) roasting the precursor to obtain gamma-Al2O3。
Specific parameters are shown in table 1.
Preparation examples 2 to 3
The same procedure as in preparation example 1 was repeated, except that the procedure described below was used for the step (a).
(a) Introducing CO2And (3) slowly and uniformly introducing the gas into the sodium aluminate solution, slowly mixing, and fully contacting to form gel to obtain the pseudoboehmite.
Specific parameters are shown in table 1.
TABLE 1
| Serial number | Preparation example 1 | Preparation example 2 | Preparation example 3 |
| Concentration of sodium aluminate solution (mol/L) | 1.2 | 1.0 | 1.2 |
| Gel forming temperature (. degree. C.) | 60 | 60 | 60 |
| pH of gel formation | 10 | 10 | 10 |
| Aging temperature (. degree.C.) | 90 | 90 | 90 |
| Aged pH | 10.2 | 10.5 | 10.2 |
| Aging time (h) | 4 | 4 | 4 |
| Drying temperature (. degree.C.) | 105 | 105 | 105 |
| Drying time (h) | 4 | 4 | 4 |
| Calcination temperature (. degree.C.) | 500 | 500 | 550 |
| Calcination time (h) | 4 | 4 | 4 |
Note: the sodium aluminate solution concentration is calculated as alumina.
Examples 1 to 2 and comparative example 1
The raw materials shown in table 2 were mixed uniformly and molded to obtain a green body. And drying the blank at 100 ℃ by adopting a hot air method to obtain a dried blank. Roasting the dried green body: heating to a first roasting temperature at a heating rate of 6 ℃/min, and roasting at the first roasting temperature for 2 hours at a constant temperature; and then heating to a second roasting temperature at the temperature rise speed of 8 ℃/min, roasting at the second roasting temperature for 2 hours at constant temperature, and cooling to obtain the carbonyl sulfide hydrolysis catalyst.
TABLE 2
| Example 1 | Example 2 | Comparative example 1 | |
| γ-Al2O3Preparation example 1 | 70 parts by weight | — | — |
| γ-Al2O3(preparation example 2) | — | — | 72 parts by weight |
| γ-Al2O3Preparation example 3 | — | 70 parts by weight | — |
| Titanium dioxide | 2 parts by weight of | 2 parts by weight of | 2 parts by weight of |
| Cobalt nitrate | — | — | 2 parts by weight of |
| Potassium carbonate | 10 parts by weight | 10 parts by weight | 10 parts by weight |
| Polyvinyl alcohol | 3 parts by weight of | 4 parts by weight of | 3 parts by weight of |
| Carboxymethyl cellulose | 2 parts by weight of | 2 parts by weight of | 2 parts by weight of |
| Ammonium bicarbonate | 5 parts by weight of | 5 parts by weight of | 3 parts by weight of |
| Nitric acid | 3 parts by weight of | — | 2 parts by weight of |
| Acetic acid | — | 3 weight percentPortions are | — |
| Water (W) | 5 parts by weight of | 4 parts by weight of | 4 parts by weight of |
| Form of molding | Kneading and extruding method | Rotating ball forming method | Kneading and extruding method |
| Shape of the blank | Columnar shape | Spherical shape | Columnar shape |
| First roasting temperature | 450℃ | 420℃ | 500℃ |
| Second roasting temperature | 600℃ | 550℃ | 580℃ |
Comparative example 2
The carbonyl sulfide hydrolysis catalyst was prepared according to the method of CN101108339A embodiment 3.
Examples of the experiments
The performance of the carbonyl sulfide hydrolysis catalyst was tested using the following method: filling carbonyl sulfide hydrolysis catalyst into a fixed bed for reactionIn the reactor, the concentration of carbonyl sulfide in inlet flue gas is 200ppm, the water content is 0.1 wt%, and the space velocity is 3000h-1And the temperature is 80 ℃, and the performance of the carbonyl sulfide hydrolysis catalyst is tested. The results obtained are shown in Table 3.
The carbonyl sulfide hydrolysis rate is calculated as follows:
the carbonyl sulfide (COS) hydrolysis rate refers to the ratio of COS, which is subjected to a hydrolysis reaction, to the amount of imported COS, and is calculated as follows:
in the formula etacosCOS hydrolysis rate,%;
Cm-COS inlet mean concentration, ppm;
CiCOS outlet concentration (i ═ 1,2,3, …), ppm.
The hydrogen sulfide generation rate was calculated as follows:
hydrogen sulfide (H)2S) production rate means H produced by actual hydrolysis2S accounts for the theoretical complete hydrolysis of COS to H2The ratio of the amount of S is calculated as follows:
in the formula etaH2S—H2S formation rate,%;
Cntheoretically complete hydrolysis of COS to H2Average concentration of S, ppm;
Cj—H2s outlet concentration (i ═ 1,2,3, …), ppm
TABLE 3
As can be seen from the data in Table 3, the hydrogen sulfide generation rate of the present invention can reach more than 99% within 5 hours, which indicates that the hydrogen sulfide is rapidly desorbed from the inner surface of the catalyst and diffused into the main gas phase body while the carbonyl sulfide is hydrolyzed to generate hydrogen sulfide, thereby reducing the deposition of sulfur and reducing the poisoning chance of the carbonyl sulfide hydrolysis catalyst.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. The carbonyl sulfide hydrolysis catalyst is characterized by being prepared from the following raw materials:
wherein, the gamma-Al2O3The preparation method comprises the following steps:
(a) gelatinizing an aluminate solution at the temperature of 50-75 ℃ and the pH of 9.5-12 to form pseudo-boehmite;
(b) aging pseudo-boehmite at the temperature of 80-105 ℃ and the pH value of 10-12.5 to obtain a crystal;
(c) washing the crystal, and drying at 80-120 ℃ to obtain a precursor;
(d) roasting the precursor at 350-650 ℃ to obtain gamma-Al2O3。
2. The carbonyl sulfide hydrolysis catalyst according to claim 1, wherein the weight ratio of the polyvinyl alcohol, the carboxymethyl cellulose and the ammonium bicarbonate is (3-6) to 2 (4-7).
3. The carbonyl sulfide hydrolysis catalyst of claim 1, wherein the potassium oxide precursor is potassium carbonate and the titanium-containing material is titanium dioxide.
4. The carbonyl sulfide hydrolysis catalyst according to claim 1, wherein the concentration of the aluminate solution is 0.5 to 2mol/L calculated on alumina;
reacting an aluminate solution with an acidic substance to form a pseudoboehmite; wherein the acidic substance is selected from sulfuric acid solution or acidic liquid formed by introducing carbon dioxide into water.
5. The carbonyl sulfide hydrolysis catalyst as claimed in claim 1, wherein the aging time is 2-8 h, the drying time is 2-9 h, and the calcination time is 2-8 h.
6. The carbonyl sulfide hydrolysis catalyst of claim 1, wherein the binder is selected from one or more of sesbania powder, citric acid, nitric acid, acetic acid, or water.
7. A carbonyl sulfide hydrolysis catalyst according to any of claims 1 to 6, wherein the aluminate in the aluminate solution is selected from one or more of sodium aluminate or potassium aluminate.
8. A method for preparing a carbonyl sulfide hydrolysis catalyst as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) will comprise gamma-Al2O3Mixing the raw materials of titanium-containing substance, potassium oxide precursor, polyvinyl alcohol, carboxymethyl cellulose, ammonium bicarbonate and binder, and molding to obtain a blank;
(2) drying the green body by adopting a hot air method to obtain a dried green body;
(3) roasting the dried green body: heating to 400-500 ℃ at a heating rate of 3-10 ℃/min, and roasting at a constant temperature for 1-5 h; then heating to 500-650 ℃ at the heating rate of 5-13 ℃/min, and roasting at constant temperature for 1-5 h; cooling to obtain the carbonyl sulfide hydrolysis catalyst.
9. The method according to claim 8, wherein the drying temperature is 80 to 120 ℃.
10. According to the claimsThe method of claim 8, further comprising preparing γ -Al2O3The steps of (1):
(a) gelatinizing an aluminate solution at the temperature of 50-75 ℃ and the pH of 9.5-12 to form pseudo-boehmite;
(b) aging pseudo-boehmite at the temperature of 80-105 ℃ and the pH value of 10-12.5 to obtain a crystal;
(c) washing the crystal, and drying at 80-120 ℃ to obtain a precursor;
(d) roasting the precursor at 350-650 ℃ to obtain gamma-Al2O3。
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| CN113976101A (en) * | 2021-11-15 | 2022-01-28 | 中国科学院山西煤炭化学研究所 | Supported carbonyl sulfide hydrolysis catalyst and preparation method and application thereof |
| CN114367279A (en) * | 2021-12-31 | 2022-04-19 | 东南大学 | Low-temperature poisoning-resistant hydrolysis catalyst for fine desulfurization of blast furnace gas and preparation method thereof |
| WO2023273274A1 (en) * | 2021-06-28 | 2023-01-05 | 中晶环境科技股份有限公司 | Carbonyl sulfide hydrolysis catalyst and preparation method therefor |
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| CN1212237A (en) * | 1997-09-19 | 1999-03-31 | 中国科学院山西煤炭化学研究所 | Method for preparing active aluminum oxide by sodium aluminate carbonating process |
| CN101108339A (en) * | 2007-07-25 | 2008-01-23 | 太原理工大学 | Intermediate temperate carbonyl sulfur hydrolyst and method of preparing the same and use thereof |
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| JP2002224572A (en) * | 2001-01-31 | 2002-08-13 | Kawasaki Steel Corp | Catalyst for hydrolyzing carbonyl sulfide and method for hydrolyzing carbonyl sulfide |
| CN113441124A (en) * | 2021-06-28 | 2021-09-28 | 中晶环境科技股份有限公司 | Carbonyl sulfide hydrolysis catalyst and preparation method thereof |
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| CN1212237A (en) * | 1997-09-19 | 1999-03-31 | 中国科学院山西煤炭化学研究所 | Method for preparing active aluminum oxide by sodium aluminate carbonating process |
| CN101108339A (en) * | 2007-07-25 | 2008-01-23 | 太原理工大学 | Intermediate temperate carbonyl sulfur hydrolyst and method of preparing the same and use thereof |
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| WO2023273274A1 (en) * | 2021-06-28 | 2023-01-05 | 中晶环境科技股份有限公司 | Carbonyl sulfide hydrolysis catalyst and preparation method therefor |
| CN113976101A (en) * | 2021-11-15 | 2022-01-28 | 中国科学院山西煤炭化学研究所 | Supported carbonyl sulfide hydrolysis catalyst and preparation method and application thereof |
| CN114367279A (en) * | 2021-12-31 | 2022-04-19 | 东南大学 | Low-temperature poisoning-resistant hydrolysis catalyst for fine desulfurization of blast furnace gas and preparation method thereof |
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