CN113181953A - Organic sulfur hydrolysis catalyst for coke oven gas and preparation method thereof - Google Patents
Organic sulfur hydrolysis catalyst for coke oven gas and preparation method thereof Download PDFInfo
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- CN113181953A CN113181953A CN202110444212.9A CN202110444212A CN113181953A CN 113181953 A CN113181953 A CN 113181953A CN 202110444212 A CN202110444212 A CN 202110444212A CN 113181953 A CN113181953 A CN 113181953A
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- catalyst
- organic sulfur
- hydroxide
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 125000001741 organic sulfur group Chemical group 0.000 title claims abstract description 32
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 27
- 239000000571 coke Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 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 6
- 238000003980 solgel method Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 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 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—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
- 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
- B01J35/61—Surface area
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The organic sulfur hydrolysis catalyst for coke oven gas and the preparation method thereof comprise the following components in parts by weight: 0.001-10 parts of active component nitrate, 0.1-20 parts of alkali metal compound, 0.1-20 parts of alkaline earth metal compound, 170-99 parts of catalyst carrier Silicalite with MFI structure and 0.01-100 parts of deionized water. The organic sulfur hydrolysis catalyst and the preparation method thereof adopt the catalyst carrier Silicalite-1 with MFI structure as the catalyst carrier, alkali metal, alkaline earth metal and other active metal components have synergistic effect, and are suitable for the raw material gas containing saturated vapor, and the hydrophobic porous catalyst carrier Silicalite-1 with MFI structure enables organic sulfur to be adsorbed on alkaline active sites loaded on the carrier, thereby further catalyzing hydrolysis and improving the conversion speed and conversion rate of the organic sulfur.
Description
Technical Field
The invention belongs to the technical field of organic sulfur hydrolysis catalysts, and particularly relates to an organic sulfur hydrolysis catalyst for coke oven gas and a preparation method thereof.
Background
Compared with oxidation and hydrogenolysis methods, the catalytic hydrolysis method has many advantages and avoids adsorptionThe method has the advantages of solving the problem that the precision and the sulfur capacity cannot be simultaneously met during the removal of COS, and having good prospect. In the prior art, pure gamma-Al 2O3 is used as a catalyst, and the hydrolysis conversion rate of COS can reach 51.2%. In addition, the prior art is an activated alumina catalyst without any auxiliary agent, but the catalyst has poor sulfate resistance, is easy to deactivate, has frequent catalyst replacement times, and increases the cost of the desulfurization process. Introduction to the prior art by TiO2The sulfate resistance of the supported catalyst is enhanced, but it is difficult to obtain a catalyst having a high specific surface area. In the prior art, alumina is taken as a carrier, potassium carbonate and ammonium molybdate are respectively taken as a hydrolysis active component and a deoxidation active component, and the defects are that the reaction temperature is 200-300 ℃, and certain requirements are provided for the sulfur content in raw material gas. In the prior art, excessive carbonyl sulfide and the like in converted gas are removed by taking activated carbon as a carrier, the operation condition does not need heating and pressurizing, but the sulfur capacity is too small, and the generated H2S is adsorbed by the activated carbon, so that the adsorption and hydrolysis reaction of COS is hindered.
In the coke oven gas, because the raw gas contains saturated vapor, the traditional catalyst preferentially adsorbs water molecules, so that organic sulfur cannot be adsorbed to an active site and cannot be activated for further hydrolysis, the polarity of the generated hydrogen sulfide is better than that of the organic sulfur and is preferentially adsorbed, so that the hydrolysis reaction cannot be completely carried out, and the conversion rate cannot be improved. In view of the above problems, it is important to develop a sulfuric acid-resistant organosulfur hydrolysis catalyst having a high specific surface area and a hydrophobic property.
Disclosure of Invention
The invention aims to provide a coke oven gas organic sulfur hydrolysis catalyst and a preparation method thereof, and aims to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the organic sulfur hydrolysis catalyst for the coke oven gas comprises the following components in parts by weight: 0.001-10 parts of active component nitrate, 0.1-20 parts of alkali metal compound, 0.1-20 parts of alkaline earth metal compound, 170-99 parts of catalyst carrier Silicalite with MFI structure and 0.01-100 parts of deionized water.
Further, the nitrate as the active component is at least one element selected from IIIA, IB, IIB, IVB, VIB, VIIB, VIII and rare earth elements; the Silicalite-1 of the catalyst carrier with the MFI structure is a hydrophobic porous structure with high specific surface and porous communication.
Further, the alkali metal compound includes an oxide, hydroxide, carbonate or bicarbonate of an alkali metal; the oxide of an alkali metal includes sodium oxide, potassium oxide, cesium oxide, or lithium oxide; the hydroxide includes sodium hydroxide, potassium hydroxide, cesium hydroxide or lithium hydroxide; the carbonate comprises sodium carbonate, potassium carbonate, cesium carbonate or lithium carbonate; the bicarbonate includes sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, or lithium bicarbonate.
Further, the alkaline earth metal compound includes a hydroxide or an oxide of an alkaline earth metal, and the hydroxide includes magnesium hydroxide, calcium hydroxide, or barium hydroxide; the oxide includes magnesium oxide, calcium oxide or barium oxide.
Further, the preparation method of the coke oven gas organic sulfur hydrolysis catalyst comprises the following steps:
step 1: sequentially washing silicalite-1 with an MFI structure with distilled water for 3-4 times until filtrate is neutral, and drying in an air-blast drying oven after suction filtration;
step 2: boiling the dried silicalite-1 with the MFI structure in an aqueous solution of an alkali metal compound for 0.5-5 h, washing the filtrate with distilled water until the filtrate is neutral, and drying the filtrate in a forced air drying oven for later use after suction filtration;
and step 3: preparing active components by sol-gel method, preparing active metal nitrate aqueous solution with different concentrations, and adding proper amount of N2CO3Mixing the solutions, just completely immersing the molecular sieve carrier into hydrosol, drying in an oven after ultrasonic immersion, and then roasting in a muffle furnace by taking air as carrier gas;
and 4, step 4: soaking the roasted catalyst in alkaline earth metal alkaline aqueous solution in the same volume, soaking the catalyst in ultrasonic for 0.5 to 5 hours, and drying the catalyst in an oven for 4 to 15 hours to obtain the organic sulfur hydrolysis catalyst.
Further, the drying temperature of the step 1 is 40-120 ℃, and the drying time is 12 hours.
Further, in the step 2, the concentration of the alkali metal compound aqueous solution is 1-20%; the drying temperature is 40-120 ℃, and the drying time is 12 hours.
Further, in the step 2 and the step 3, the concentration of the active metal nitrate aqueous solution is 1% -10%; the ultrasonic dipping time is 30-60 minutes; the roasting temperature is 300-550 ℃, and the roasting time is 5 hours.
Further, in step 4, the alkaline aqueous solution of alkaline earth metal has a concentration of 1 to 20%.
Compared with the prior art, the invention has the following technical effects:
the organic sulfur hydrolysis catalyst and the preparation method thereof adopt the catalyst carrier Silicalite-1 with MFI structure as the catalyst carrier, alkali metal, alkaline earth metal and other active metal components have synergistic effect, and are suitable for the raw material gas containing saturated vapor, and the hydrophobic porous catalyst carrier Silicalite-1 with MFI structure enables organic sulfur to be adsorbed on alkaline active sites loaded on the carrier, thereby further catalyzing hydrolysis and improving the conversion speed and conversion rate of the organic sulfur. The Silicalite-1 carrier with the MFI structure, which has a high specific surface and is communicated with the pores, avoids sulfur deposition to reduce the activity of the catalyst, and the carrier pore walls under high-temperature saturated water vapor can not collapse to maintain the high specific surface and have multiple active sites. Active metal component for inhibiting generation of H by catalytic hydrolysis of organic sulfur2S is further oxidized into sulfur dioxide and sulfate radical, and the sulfur dioxide and the sulfate radical are combined with alkali metal and alkaline earth metal to generate sulfate, so that the catalyst is deactivated. The catalyst can be converted at 90 ℃ to contain 1000mg/m3The simulated raw gas of COS has the space velocity of 10000h < -1 >, the relative humidity of 100 percent, the organic sulfur conversion rate of 100 percent and the maintenance time of 6 hours, and shows good organic sulfur conversion activity and functions of sulfation resistance and sulfur deposition resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of implementation examples of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The organic sulfur hydrolysis catalyst comprises the following components in parts by weight: 0.001-10 parts of active component nitrate, 0.1-20 parts of alkali metal compound, 0.1-20 parts of alkaline earth metal compound, 170-99 parts of catalyst carrier Silicalite with MFI structure and 0.01-100 parts of deionized water. The Silicalite-1 of the catalyst carrier with the MFI structure is a hydrophobic porous structure with high specific surface and porous communication.
The catalyst carrier Silicalite-1 with MFI structure was purchased from: tianjin south China catalyst Co., Ltd, Shanghai Shen cloud-shaped environment-friendly new material Co., Ltd.
The nitrate as the active component comprises at least one of IIIA, IB, IIB, IVB, VIB, VIIB, VIII elements and rare earth elements. IIIA is mainly Al element, IB is mainly Cu and Ag, IIB is mainly Zn, IVB is mainly Ti and Zr, VIB is mainly Cr and Mo, VIIB is mainly Mn, VIII is mainly Fe, Co, Ni, Ru, Rh, Pd and Pt.
The alkali metal compound includes oxides, hydroxides, carbonates and bicarbonates of alkali metals; the alkali metal oxide includes sodium oxide, potassium oxide, cesium oxide, and lithium oxide; the hydroxides include sodium hydroxide, potassium hydroxide, cesium hydroxide, and lithium hydroxide; the carbonate includes sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate; the bicarbonate includes sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, and lithium bicarbonate.
The alkaline earth metal compound comprises hydroxides and oxides of alkaline earth metals, and the hydroxides comprise magnesium hydroxide, calcium hydroxide and barium hydroxide; the oxides include magnesium oxide, calcium oxide, and barium oxide.
The catalyst is prepared by sol-gel and isovolumetric impregnation methods.
The invention also provides a preparation method of the organic sulfur hydrolysis catalyst, which comprises the following steps:
the method comprises the following steps: sequentially washing the Silicalite-1 with the MFI structure with distilled water for 3-4 times until filtrate is neutral, and drying in an air-blast drying oven after suction filtration;
step two: boiling the dried carrier in an alkali metal compound aqueous solution for a period of time, washing the carrier with distilled water until filtrate is neutral, and drying the carrier in a forced air drying oven for later use after suction filtration;
step three: preparing active components by sol-gel method, preparing active metal nitrate aqueous solution with different concentrations, and adding proper amount of N2CO3Mixing the solutions, just completely immersing the molecular sieve carrier into hydrosol, ultrasonically immersing for a certain time, drying in an oven, and roasting in a muffle furnace at a certain temperature by taking air as carrier gas;
step four: soaking the roasted catalyst in alkaline earth metal aqueous solution with certain concentration in the same volume, soaking for a certain time by ultrasonic wave, and drying in an oven for a certain time to obtain the final required catalyst.
The drying temperature in the step one is 40-120 ℃, and the drying time is 12 hours.
And the concentration of the alkali metal compound aqueous solution in the second step is 1-20%.
And the drying temperature in the second step is 40-120 ℃, and the drying time is 12 hours.
And step three, the concentration of the active metal nitrate aqueous solution is 1-10%.
And step three, the ultrasonic dipping time is 30-60 minutes.
And step three, the roasting temperature is 300 ℃ and 550 ℃, and the roasting time is 5 hours.
And fourthly, the concentration of the alkaline earth metal alkaline aqueous solution is 1-20%.
Example 1
Weighing 20g of silicalite-1 with the MFI structure as a catalyst carrier, sequentially washing the silicalite-1 with tap water and distilled water for 3-4 times until the filtrate is neutral, performing suction filtration, and drying the filtrate in a forced air drying oven at 120 ℃ for 9 hours; boiling the dried carrier in 100ml of 10% KOH aqueous solution for 1.5 hours, washing the carrier by using distilled water until the filtrate is neutral, and drying the carrier in an air drying oven at 120 ℃ for later use after suction filtration; preparing active components by a sol-gel method, preparing 30g of 5% ferric nitrate aqueous solution, and adding 10g of 10% N2CO3Mixing the solutions to formCompletely immersing the molecular sieve carrier into hydrosol, ultrasonically immersing for 30 minutes, drying in an oven at 120 ℃ for 5 hours, and then roasting in a muffle furnace at 300 ℃ for 5 hours by taking air as carrier gas; an equal volume of calcined catalyst was impregnated with 26g 7% Mg (OH)2And (3) soaking the catalyst in the aqueous solution for 30 minutes by ultrasonic waves, and drying the soaked catalyst in an oven for 120 hours to obtain the final required catalyst.
Example 2
Weighing 20g of silicalite-1 with the MFI structure as a catalyst carrier, sequentially washing the silicalite-1 with tap water and distilled water for 3-4 times until the filtrate is neutral, performing suction filtration, and drying the filtrate in a forced air drying oven at 100 ℃ for 12 hours; boiling the dried carrier in 100ml of 10% NaOH aqueous solution for 1.5 hours, washing the carrier with distilled water until the filtrate is neutral, and drying the carrier in a forced air drying oven at 100 ℃ for later use after suction filtration; preparing active components by a sol-gel method, preparing 30g of mixed aqueous solution of 4 percent ferric nitrate and 1 percent cobalt nitrate, and adding 9.5g of 10 percent N2CO3Mixing the solution to form sol, completely immersing the molecular sieve carrier into the hydrosol, ultrasonically immersing for 60 minutes, drying in an oven at 100 ℃ for 7 hours, and then roasting in a muffle furnace at 400 ℃ for 5 hours by taking air as carrier gas; an equal volume of calcined catalyst was impregnated with 26g of 7% Ca (OH)2And (3) soaking in the aqueous solution for 30 minutes by ultrasonic waves, and drying in an oven at 120 ℃ for 12 hours to obtain the final required catalyst.
Example 3
Weighing 20g of silicalite-1 with the MFI structure as a catalyst carrier, sequentially washing the silicalite-1 with tap water and distilled water for 3-4 times until the filtrate is neutral, performing suction filtration, and drying the filtrate in a forced air drying oven at 110 ℃ for 10 hours; boiling the dried carrier in 100ml of 5% NaOH aqueous solution for 2 hours, washing the carrier with distilled water until the filtrate is neutral, and drying the carrier in a forced air drying oven at 100 ℃ for later use after suction filtration; preparing active components by a sol-gel method, preparing 30g of mixed aqueous solution of 4% copper nitrate, 1% aluminum nitrate and 0.5% cerium nitrate, and adding 7.5g of 10% N2CO3Mixing the solution to form sol, completely immersing the molecular sieve carrier into the hydrosol, ultrasonically immersing for 60 minutes, drying in an oven at 90 ℃ for 12 hours, and then roasting in a muffle furnace at 500 ℃ for 3 hours by taking air as carrier gas; calcined catalystAn equal volume of the solution was immersed in 26g 10% Ba (OH)2And (3) soaking the catalyst in the aqueous solution for 50 minutes by ultrasonic waves, and drying the soaked catalyst in an oven at 120 ℃ for 12 hours to obtain the finally required catalyst.
EXAMPLES COMPARATIVE TABLE
| Ambient temperature | Humidity | Reforming gas | Conversion rate | Maintenance time | |
| Example 1 | 90℃ | 90％ | 1000mg/m3COS | 100％ | 5.5h |
| Example 2 | 90℃ | 100％ | 1000mg/m3COS | 100％ | 6h |
| Example 3 | 90℃ | 90％ | 1000mg/m3COS | 100％ | 5.5h |
The catalyst contains 1000mg/m at 90 deg.C3The simulated raw gas of COS has the space velocity of 10000h < -1 >, the relative humidity of 100 percent, the organic sulfur conversion rate of 100 percent and the maintenance time of 6 hours, and shows good organic sulfur conversion activity and functions of sulfation resistance and sulfur deposition resistance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, substitutions, modifications and variations may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The organic sulfur hydrolysis catalyst for the coke oven gas is characterized by comprising the following components in parts by weight: 0.001-10 parts of active component nitrate, 0.1-20 parts of alkali metal compound, 0.1-20 parts of alkaline earth metal compound, 170-99 parts of catalyst carrier Silicalite with MFI structure and 0.01-100 parts of deionized water.
2. The coke oven gas organic sulfur hydrolysis catalyst as claimed in claim 1, wherein the active component nitrate is at least one selected from IIIA, IB, IIB, IVB, VIB, VIIB, VIII elements or rare earth elements; the Silicalite-1 of the catalyst carrier with the MFI structure is Silicalite with an MFI framework structure.
3. The coke oven gas organosulfur hydrolysis catalyst of claim 1, wherein the alkali metal compound comprises an oxide, hydroxide, carbonate or bicarbonate of an alkali metal; the oxide of an alkali metal includes sodium oxide, potassium oxide, cesium oxide, or lithium oxide; the hydroxide includes sodium hydroxide, potassium hydroxide, cesium hydroxide or lithium hydroxide; the carbonate comprises sodium carbonate, potassium carbonate, cesium carbonate or lithium carbonate; the bicarbonate includes sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, or lithium bicarbonate.
4. The coke oven gas organic sulfur hydrolysis catalyst of claim 1, wherein the alkaline earth metal compound comprises a hydroxide or an oxide of an alkaline earth metal, the hydroxide comprising magnesium hydroxide, calcium hydroxide or barium hydroxide; the oxide includes magnesium oxide, calcium oxide or barium oxide.
5. The method for preparing the catalyst for hydrolyzing organic sulfur in coke oven gas as claimed in any one of claims 1 to 4, comprising the steps of:
step 1: sequentially washing silicalite-1 with an MFI structure with distilled water for 3-4 times until filtrate is neutral, and drying in an air-blast drying oven after suction filtration;
step 2: boiling the dried carrier in an alkali metal compound aqueous solution for 0.5-5 h, washing with distilled water until the filtrate is neutral, and drying in a forced air drying oven for later use after suction filtration;
and step 3: preparing active components by sol-gel method, preparing active metal nitrate aqueous solution with different concentrations, and adding proper amount of N2CO3Mixing the solutions, just completely immersing the molecular sieve carrier into hydrosol, drying in an oven after ultrasonic immersion, and then roasting in a muffle furnace by taking air as carrier gas;
and 4, step 4: soaking the roasted catalyst in alkaline earth metal alkaline aqueous solution in the same volume, soaking the catalyst in ultrasonic for 0.5 to 5 hours, and drying the catalyst in an oven for 4 to 15 hours to obtain the organic sulfur hydrolysis catalyst.
6. The method for preparing the catalyst for hydrolyzing organic sulfur in coke oven gas as claimed in claim 5, wherein the drying temperature in step 1 is 40-120 ℃ and the drying time is 12 hours.
7. The method for preparing the catalyst for hydrolyzing organic sulfur in coke oven gas as claimed in claim 5, wherein in the step 2, the concentration of the aqueous solution of the alkali metal compound is 1% -20%; the drying temperature is 40-120 ℃, and the drying time is 12 hours.
8. The method for preparing the coke oven gas organic sulfur hydrolysis catalyst according to claim 5, wherein in the step 2, in the step 3, the concentration of the active metal nitrate aqueous solution is 1% -10%; the ultrasonic dipping time is 30-60 minutes; the roasting temperature is 300-550 ℃, and the roasting time is 5 hours.
9. The method for preparing the catalyst for hydrolyzing organic sulfur in coke oven gas as claimed in claim 5, wherein in the step 4, the concentration of alkaline earth metal alkaline aqueous solution is 1-20%.
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