CN114471522A - High specific surface area anti-poisoning blast furnace gas hydrolysis catalyst and preparation method thereof - Google Patents
High specific surface area anti-poisoning blast furnace gas hydrolysis catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN114471522A CN114471522A CN202111669164.XA CN202111669164A CN114471522A CN 114471522 A CN114471522 A CN 114471522A CN 202111669164 A CN202111669164 A CN 202111669164A CN 114471522 A CN114471522 A CN 114471522A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- surface area
- specific surface
- poisoning
- blast furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 42
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 231100000572 poisoning Toxicity 0.000 claims description 15
- 230000000607 poisoning effect Effects 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 11
- 239000011148 porous material Substances 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 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 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical group O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 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
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- 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
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high specific surface area anti-poisoning blast furnace gas hydrolysis catalyst and a preparation method thereof, wherein the catalyst takes gamma alumina as a carrier, an oxide of alkali metal as an active component and an oxide of rare earth metal as an auxiliary agent, and a plurality of pore-forming agents are added in the preparation process; the preparation method comprises the steps of dissolving the aluminum precursor, the alkali precursor, the rare earth metal precursor and the pore-expanding agent in deionized water, uniformly stirring, adding ammonia water in batches and slowly in the ultrasonic stirring process to adjust the pH until the precipitation is complete, standing, heating, stirring, drying, grinding and calcining to obtain the aluminum-based composite materialObtaining the COS hydrolysis catalyst. Has the advantages that the COS hydrolysis catalyst prepared by adding the pore-expanding agent, the rare earth metal and the alkali metal has higher specific surface area and more macroporous structures, and can realize higher COS hydrolysis conversion rate and H at 75 DEG C2S yield and long service life; meanwhile, the preparation method is simple and convenient and is easy to operate.
Description
The technical field is as follows:
the invention belongs to the field of hydrolysis catalysis of blast furnace gas, and particularly relates to high-specific-surface-area low-temperature poisoning-resistant COS hydrolysis catalysis of the blast furnace gas and a preparation method thereof.
Background art:
with the promulgation of the regulations of 'opinion about promoting and implementing ultra-low emission of the iron and steel industry', etc., the iron and steel industry formally enters the stage of ultra-low emission modification, and the hydrogen sulfide (H) of blast furnace gas of the iron and steel enterprise is clearly proposed in the regulations2S) concentration less than or equal to 20mg/Nm3And decarbonylation of sulfur (COS) is encouraged. Monitoring statistics show that most of inorganic sulfur in blast furnace gas is hydrogen sulfide, accounts for about 30%, most of organic sulfur is carbonyl sulfur (COS), accounts for about 70%, and trace carbon disulfide (CS2) exists, wherein the removal of organic sulfur is a main difficulty.
The hydrolysis catalysis method is the best blast furnace gas fine desulfurization technology at present due to the advantages of mild reaction conditions, high desulfurization efficiency, no by-products and the like.
The current research on catalysts is mainly focused on both metal oxide and non-metal based.
The metal oxide based hydrolysis catalysts are based mainly on gamma-Al2O3And TiO2Typically, the non-metals are primarily carbon-based catalysts.
The existing catalyst has short service life, quick inactivation and obvious adsorption effect in the purification process, and is difficult to really popularize and apply.
For example, patent CN112058273A discloses an activated carbon-based catalyst, which is characterized in that one or a combination of several of zinc oxide, iron oxide, manganese oxide and copper oxide is loaded on an activated carbon-based catalyst as an active component, and an alkali metal or alkaline earth metal oxide is used as a promoter to improve the catalytic efficiency of the catalyst. But the desulfurization mechanism of the catalyst is mainly adsorption oxidation, and when the activated carbon reaches adsorption saturation, the desulfurization efficiency is rapidly reduced.
Therefore, research and development of a COS hydrolysis catalyst with high desulfurization efficiency, long service life and simple preparation technology becomes a great hotspot in the technical research field, and has important significance for fine desulfurization of blast furnace gas.
The invention content is as follows:
the invention aims to solve the problems in the prior art, provide a high-desulfurization-efficiency long-life blast furnace gas COS hydrolysis catalyst and a preparation method thereof.
The specific technical scheme of the invention is as follows: the catalyst of the invention is prepared from gamma-Al2O3Taking alkali metal as an active ingredient and rare earth metal as an auxiliary agent as a carrier, and adding a pore-expanding agent; the mass ratio of the alkali metal, the rare earth metal, the pore-expanding agent and the carrier in the catalyst is (0.03-0.15): (0.001-0.010): (0.05-0.20): 1;
further, the alkali metal in the catalyst is one or more of Na, K and Ca.
Further, the pore-expanding agent in the catalyst is one or more of polyvinyl alcohol, polyacrylamide and dodecyl benzene sulfonic acid; the precursor of the carrier is Al (NO)3)3The precursor of the catalyst active component is K2CO3、CH3COOK、Na2CO3、CH3COONa、Ca(CH3COO)2One or more of the above; the rare earth metal in the catalyst is one or more of holmium, neodymium and lanthanum, and the precursor is one or more of nitrate, acetate and oxalate.
The invention also discloses a preparation method of the high-specific surface area anti-poisoning blast furnace gas hydrolysis catalyst, which comprises the following steps:
step one, respectively accounting for (0.03-0.15) the mass ratio of alkali metal, rare earth metal, pore-expanding agent and carrier in the catalyst: (0.001-0.010): (0.05-0.20): 1, respectively weighing a precursor of a carrier, a precursor of an alkali metal, a precursor of a rare earth metal and a pore-expanding agent according to the element mass ratio, dissolving the precursors in deionized water, and fully stirring and uniformly mixing to form emulsion to be processed;
step two, slowly adding NH in batches under the condition of ultrasonic stirring3·H2Adjusting the pH value to 8-10, and sequentially standing, heating, stirring and drying the obtained emulsion at normal temperatureGrinding and calcining to prepare the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst.
Further, in the step one, the dissolving and mixing sequence of the catalyst is that a precursor of the carrier and a precursor of the alkali metal are added, after the mixture is fully stirred and reacts, the precursor of the rare earth metal is added, and finally the pore-expanding agent is added.
Further, in the second step, the ultrasonic frequency of the ultrasonic stirring is 80-120 kHz.
Further, in the second step, NH3·H2Adding the O solution into the emulsion to be processed for 3-5 times until the pH value of the emulsion to be processed is 8-10; each time NH is added3·H2And (4) after the solution is subjected to O, ultrasonically stirring for 10-15 min until the solution is clarified again or precipitates are uniformly dispersed.
Further, in the second step, the standing at the normal temperature is specifically standing for 16-24 hours at 35-50 ℃; the heating stirring is specifically heating stirring for 5 hours, the stirring speed is 40-50 r/s, and the temperature is 60-80 ℃.
Further, in the second step, the drying process includes: drying for 22-26 h at 100-120 ℃, and then continuously drying for 10-12 h at 140-160 ℃.
Further, in the second step, the calcining comprises: calcining for 1-2 h at 300-400 ℃, and then calcining for 4-6 h at 600-750 ℃.
Compared with the prior art, the invention has the following remarkable advantages:
1. the preparation method is simple and convenient, is easy to operate, and adds a proper amount of carbonate or nitrate of the preferable pore-expanding agent and the active additive before chemical precipitation, so that the additive is uniformly wrapped in the precipitated particles in the process of adding ammonia water; a large amount of gas is decomposed and released in the drying and calcining processes, the pore structure of the catalyst is improved from the inside, and the pore-forming effect is realized, so that the specific surface area of the prepared catalyst is obviously increased, the proportion of macropores is obviously increased, the COS adsorption and the timely overflow of H2S are facilitated, and the residual oxygen of H2S in the pore is avoidedThe deposition of sulfur and sulfate is reduced, so that the catalyst has higher hydrolytic activity and stronger poisoning resistance; tests prove that the high-specific surface area anti-poisoning blast furnace gas hydrolysis catalyst can achieve 100% of desulfurization efficiency at 75 ℃, and the outlet H2The S selectivity reaches 100 percent, namely COS is completely converted into H2S, no adsorption, deposition, oxidation and the like.
2. In the catalyst, the doping of the rare earth elements supplements more reaction active sites, and the interaction of the alkali metal and the rare earth elements effectively promotes the low-temperature hydrolysis activity of the catalyst and reduces the activation temperature.
3. Controlling the adding sequence of the raw materials, preparing emulsion to be processed, adding a precursor of a carrier and a precursor of an alkali metal, fully stirring for reaction, then adding the precursor of the rare earth metal, and finally adding the pore-expanding agent; secondly, in the process of adding ammonia water, the means of adding ammonia water in a plurality of times and fully mixing the ammonia water by ultrasonic waves is adopted, so that the local flocculation caused by the excessively fast addition of the ammonia water is effectively avoided, the uniform preparation of the catalyst is further ensured, and the catalytic effect is good.
4. In the invention, the drying is firstly carried out for 24 hours at about 100 ℃ so as to fully dehydrate the sample; then drying for 12h at about 160 ℃, and fully dehydrating and etherifying the added auxiliaries such as polyvinyl alcohol and the like at the temperature; the calcination is to calcine at 300-400 ℃ for 1-2 h, then the additives such as the active additive and the pore-expanding agent are gradually decomposed, and then the temperature is raised to 600-750 ℃ for continuous calcination; according to the method, the improvement effect of the additive on the activity and the anti-poisoning performance is stimulated to the maximum extent according to the drying and calcining process matched with the characteristics of the precursor and the auxiliary agent.
Drawings
FIG. 1 is a graph of the desulfurization performance of a hydrolysis catalyst of the present invention;
FIG. 2 is a graph of the long term deterioration of the hydrolysis catalyst of the present invention;
FIG. 3 is a pore size distribution curve for a hydrolysis catalyst of the present invention.
Detailed Description
For the understanding of the present invention, the following detailed description will be given with reference to the accompanying drawings, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention. The raw materials used in the invention can be purchased from the market.
Comparative example 1
The catalyst is commercial gamma Al2O3No treatment or modification was made.
Example 1
The catalyst comprises the following raw materials: 5g of aluminum nitrate, 0.036g of polyvinyl alcohol, 0.043g of holmium nitrate and 0.216 g of potassium carbonate.
The preparation process comprises the following steps:
firstly, dissolving aluminum nitrate, potassium carbonate and holmium nitrate in 50mL of deionized water, adding polyvinyl alcohol, and fully stirring until the polyvinyl alcohol is completely dissolved; then, slowly adding 5ml of ammonia water under the ultrasonic condition of 80kHz, performing ultrasonic treatment for 10min, adding 5ml of ammonia water again after the solution is uniform, and circulating the operation until the pH value is 10. Standing the obtained emulsion at 40 deg.C for 24h, stirring at 60 deg.C for 4h in a magnetic stirrer at 60r/min, drying at 110 deg.C for 24h in an oven, taking out, grinding to below 100 mesh, and calcining at 700 deg.C in a muffle furnace for 6h to obtain polyvinyl alcohol, Ho, K, Al2O3A hydrolysis catalyst in a mass ratio of 0.05:0.001:0.05: 1.
Example 2
The catalyst comprises the following raw materials: : 5g of titanium dioxide, 0.072g of polyacrylamide, 0.214g of neodymium nitrate and 0.562g of sodium carbonate.
Firstly, dissolving aluminum nitrate, sodium carbonate and neodymium nitrate in 50mL of deionized water, adding polyacrylamide, and fully stirring until the materials are completely dissolved; then, under the ultrasonic condition of 100kHz, slowly adding 10ml of ammonia water, performing ultrasonic treatment for 8min, adding 10ml of ammonia water again after the solution is uniform, and circulating operation until the pH value is 10. Standing the obtained emulsion at 50 deg.C for 24h, stirring at 70 deg.C for 4h in magnetic stirrer at 60r/min, drying at 120 deg.C in oven for 24h, taking out, grinding to 100 mesh or below, calcining at 650 deg.C in muffle furnace for 6h to obtain polyacrylamide, Nd, Na, Al2O3A hydrolysis catalyst in a mass ratio of 0.10:0.005:0.10: 1.
Example 3
The preparation procedure was the same as in example 1, except that the catalyst starting materials were: 5g of titanium dioxide, 0.036g of dodecylbenzene sulfonic acid, 0.212g of lanthanum nitrate and 0.806g of calcium acetate.
The prepared catalyst is dodecyl benzene sulfonic acid, La, Ca and Al2O3A hydrolysis catalyst in a mass ratio of 0.05:0.005:0.15: 1.
Example 4
The preparation procedure was the same as in example 1, except that the catalyst starting materials were: 5g of titanium dioxide, 0.108g of polyacrylamide and 0.153g of potassium acetate.
The prepared catalyst is polyacrylamide, K, Al2O3A hydrolysis catalyst in a mass ratio of 0.15:0.05: 1.
Test example 1
The catalysts prepared in comparative example 1 and examples 1-4 were ground, tableted, and sieved, and 0.5ml of a 40-60 mesh sample was used in a catalytic activity test experiment. The test temperature range is 50-150 ℃. The experiment uses a steel cylinder gas to simulate the blast furnace gas, wherein COS and O2Are 0.02% and 1%, respectively, N2As a carrier gas, the total flow rate of the gas was set to 200ml/min, and the space velocity (GHSV) was 24000h-1. The mixed gas passes through a first-stage gas washing bottle filled with 50ml of pure water before passing through the reaction tube, so that H is realized2And introducing O. COS and H2S concentration was determined by GC-9860 gas chromatograph (Hao and Pu, China), SO2The results of the analyses were shown in FIG. 1, and were measured by a 350-XL Smoke Analyzer (Testo, Germany).
As can be seen from fig. 1, when the first and comparative examples 1 were used as hydrolysis catalysts, the COS removal rate was less than 50% at 75 ℃, and the H2S selectivity was 19%; the removal rate of COS is close to 100% at 150 ℃.
Second, the high specific surface area low temperature poison resistant hydrolysis catalyst prepared in example 1; COS removal rate at 75 ℃ is 80.53%, H2The S selectivity is 41 percent; the removal rate of COS is more than 90% within the temperature range of 100-150 ℃, and H2S selectivity is more than 80%;
third, the high specific surface area low temperature poison resistant hydrolysis catalyst prepared in example 2; the removal rate of COS at 75 ℃ is 95.8 percent, and H2S selectionThe selectivity is 85 percent; the removal rate of COS is more than 95% within the temperature range of 100-150 ℃, and H2The S selectivity is more than 90 percent;
fourth, the high specific surface area, low temperature, poison resistant hydrolysis catalyst prepared in example 3; COS removal rate at 75 ℃ is 97.23%, H2The S selectivity is 91%; the removal rate of COS is more than 95% within the temperature range of 100-150 ℃, and H2The S selectivity is more than 95 percent;
fifth, the high specific surface area, low temperature, poison resistant hydrolysis catalyst prepared in example 4; COS removal rate was 80.24% at 75 ℃ and H2The S selectivity was 53%; the removal rate of COS is more than 95% within the temperature range of 100-150 ℃, and H2The S selectivity is more than 90 percent;
in conclusion, the denitration catalyst prepared by the invention has a lower activation temperature and a wider activity temperature window, and the denitration efficiency of the high-specific-surface-area low-temperature poisoning-resistant hydrolysis catalyst prepared in the embodiment 1-4 can reach more than 80% at 75-150 ℃.
Test example 2
Test example 2 the catalyst obtained in example 1 was subjected to a long-term deterioration test under the same test conditions as in test example 1, and the test results are shown in fig. 2; as can be seen from FIG. 2, the hydrolysis catalyst prepared by the method has strong anti-poisoning capacity and long service life, after 110H of experiment, the removal rate of COS of the catalyst is still stabilized to be more than 90%, and the catalyst has an outlet H2The S selectivity is kept above 80%, and the catalyst prepared by the method is proved to have the capabilities of low temperature, high efficiency and poisoning resistance.
The catalysts obtained in examples 1 to 4 were subjected to BET specific surface area test using commercial alumina as a comparison, and the results of pore size distribution are shown in FIG. 3 and BET specific surface area results are shown in Table 1.
As can be seen from fig. 3, comparative example 1 has a pore diameter mainly of mesopores smaller than 4nm and a more concentrated pore size distribution.
The hydrolysis catalyst prepared by the method is taken as an example in example 3, the pore size distribution is in the range of 5-18nm, the pore size distribution is wider, and more macroporous structures are formed. The diffusion of COS and H2S gas is enhanced by more macroporous structures, which promotes the improvement of hydrolytic activity on the one hand, and the faster diffusion of H2S reduces the deposition and further oxidation of sulfur on the other hand, thereby achieving the improvement of anti-poisoning performance. The catalyst prepared by the method is proved to have wider pore size distribution and more macroporous structures.
TABLE 1 BET specific surface area test results for catalysts
The test results from fig. 3 and table 1 can be concluded: compared with the conventional alumina, the specific surface area of the catalyst is 10.6-18% higher, and the catalyst has higher specific surface area. The higher specific surface area and more macroporous structure promote the catalyst to realize higher catalytic activity and stronger poisoning resistance.
The above embodiments are merely illustrative of the technical concept and structural features of the present invention, and are intended to be implemented by those skilled in the art, but the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should fall within the scope of the present invention.
Claims (10)
1. A high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst is characterized in that: the catalyst is prepared from gamma-Al2O3Taking alkali metal as an active ingredient and rare earth metal as an auxiliary agent as a carrier, and adding a pore-expanding agent; wherein the mass ratio of the alkali metal, the rare earth metal, the pore-expanding agent and the carrier in the catalyst is (0.03-0.15): (0.001-0.010): (0.05-0.20): 1.
2. the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst of claim 1, wherein: the alkali metal in the catalyst is one or more of Na, K and Ca.
3. High specific surface area poisoning-resistant blast furnace according to claim 1The coal gas hydrolysis catalyst is characterized in that: the pore-expanding agent in the catalyst is one or more of polyvinyl alcohol, polyacrylamide and dodecyl benzene sulfonic acid; the precursor of the carrier is Al (NO)3)3The precursor of the catalyst active component is K2CO3、CH3COOK、Na2CO3、CH3COONa、Ca(CH3COO)2One or more of the above; the rare earth metal in the catalyst is one or more of holmium, neodymium and lanthanum, and the precursor is one or more of nitrate, acetate and oxalate.
4. A preparation method of a high-specific surface area anti-poisoning blast furnace gas hydrolysis catalyst is characterized by comprising the following steps: the method comprises the following steps:
step one, respectively accounting for (0.03-0.15) the mass ratio of alkali metal, rare earth metal, pore-expanding agent and carrier in the catalyst: (0.001-0.010): (0.05-0.20): 1, respectively weighing a precursor of a carrier, a precursor of an alkali metal, a precursor of a rare earth metal and a pore-expanding agent according to the element mass ratio, dissolving the precursors in deionized water, and fully stirring and uniformly mixing to form emulsion to be processed;
step two, slowly adding NH in batches under the condition of ultrasonic stirring3·H2And O, adjusting the pH value to 8-10, and sequentially standing the obtained emulsion at normal temperature, heating, stirring, drying, grinding and calcining to obtain the anti-poisoning blast furnace gas hydrolysis catalyst with high specific surface area.
5. The method for preparing the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst according to claim 4, wherein: in the first step, the dissolving and mixing sequence of the catalyst is that the precursor of the carrier and the precursor of the alkali metal are added firstly, the precursor of the rare earth metal is added after the full stirring reaction, and finally the pore-expanding agent is added.
6. The method for preparing the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst according to claim 4, wherein: in the second step, the ultrasonic frequency of the ultrasonic stirring is 80-120 kHz.
7. The method for preparing the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst according to claim 4, wherein: in the second step, NH3·H2Adding the O solution into the emulsion to be processed for 3-5 times until the pH value of the emulsion to be processed is 8-10; each time NH is added3·H2And (4) after the solution is subjected to O, ultrasonically stirring for 10-15 min until the solution is clarified again or precipitates are uniformly dispersed.
8. The method for preparing the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst according to claim 4, wherein: in the second step, the normal-temperature standing is specifically standing for 16-24 hours at 35-50 ℃; the heating stirring is specifically heating stirring for 5 hours, the stirring speed is 40-50 r/s, and the temperature is 60-80 ℃.
9. The method for preparing the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst according to claim 4, wherein: in the second step, the drying process includes: drying for 22-26 h at 100-120 ℃, and then continuously drying for 10-12 h at 140-160 ℃.
10. The method for preparing the high specific surface area poisoning-resistant blast furnace gas hydrolysis catalyst according to claim 4, wherein: in the second step, the calcining comprises: calcining for 1-2 h at 300-400 ℃, and then calcining for 4-6 h at 600-750 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111669164.XA CN114471522A (en) | 2021-12-31 | 2021-12-31 | High specific surface area anti-poisoning blast furnace gas hydrolysis catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111669164.XA CN114471522A (en) | 2021-12-31 | 2021-12-31 | High specific surface area anti-poisoning blast furnace gas hydrolysis catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114471522A true CN114471522A (en) | 2022-05-13 |
Family
ID=81497316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111669164.XA Pending CN114471522A (en) | 2021-12-31 | 2021-12-31 | High specific surface area anti-poisoning blast furnace gas hydrolysis catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114471522A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646556A (en) * | 2022-10-26 | 2023-01-31 | 北京北科环境工程有限公司 | Method for regenerating organic sulfur hydrolytic agent of blast furnace gas |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680025A (en) * | 2005-01-19 | 2005-10-12 | 太原理工大学 | Low-temperature hydrolyst for high concentrated organosulfur and preparation thereof |
| 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 |
| CN106031868A (en) * | 2015-03-19 | 2016-10-19 | 中国石油天然气股份有限公司 | Catalyst for hydrolysis of carbonyl sulfide as well as preparation method and application thereof |
| CN111068642A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for removing mercaptan in natural gas and preparation method thereof |
| CN113289602A (en) * | 2021-06-01 | 2021-08-24 | 清华大学 | Catalyst for carbonyl sulfide hydrolysis in blast furnace gas and preparation method and application thereof |
-
2021
- 2021-12-31 CN CN202111669164.XA patent/CN114471522A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1680025A (en) * | 2005-01-19 | 2005-10-12 | 太原理工大学 | Low-temperature hydrolyst for high concentrated organosulfur and preparation thereof |
| 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 |
| CN106031868A (en) * | 2015-03-19 | 2016-10-19 | 中国石油天然气股份有限公司 | Catalyst for hydrolysis of carbonyl sulfide as well as preparation method and application thereof |
| CN111068642A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for removing mercaptan in natural gas and preparation method thereof |
| CN113289602A (en) * | 2021-06-01 | 2021-08-24 | 清华大学 | Catalyst for carbonyl sulfide hydrolysis in blast furnace gas and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| E.Д.拉钦科，等: "《炼油工业加氢催化剂》", 中国石化出版社, pages: 149 - 150 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646556A (en) * | 2022-10-26 | 2023-01-31 | 北京北科环境工程有限公司 | Method for regenerating organic sulfur hydrolytic agent of blast furnace gas |
| CN115646556B (en) * | 2022-10-26 | 2023-12-08 | 北京北科环境工程有限公司 | Method for regenerating organic sulfur hydrolytic agent of blast furnace gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101845306B (en) | Preparation method and application of Lal-xSrxCoO3 perovskite catalyst | |
| WO2015149499A1 (en) | Low-temperature and highly efficient denitration catalyst and preparation method therefor | |
| CN112547129B (en) | Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method and application thereof | |
| CN102553574B (en) | Method for preparing flue gas SCR (Selective Catalytic Reduction) denitration catalyst | |
| CN108325549A (en) | It is a kind of for the transition metal of purifying formaldehyde and nitrogen co-doped carbon composite and preparation method thereof | |
| CN102151585B (en) | Melamine-supported denitration catalyst and preparation method thereof | |
| CN107126959B (en) | A kind of attapulgite load CoTiO3-CeO2Hetero-junctions SCR low-temperature denitration catalyst and preparation method thereof | |
| CN102389791A (en) | Desulfurization and denitrification catalyst taking kaolin as carrier and preparation method thereof | |
| CN106268787A (en) | A kind of samarium doping MnOxlow-temperature SCR catalyst and its preparation method and application | |
| CN110773153B (en) | Supported manganese-based medium-low temperature denitration catalyst, preparation method and application thereof | |
| CN103657632B (en) | A kind of base extraction monoblock type chromium oxide catalyst and preparation method and application | |
| CN109701547B (en) | Preparation method of manganese cerium catalyst with high methane catalytic activity and product | |
| CN101773780A (en) | Method for depriving nitric oxide by plasma cooperating with low-temperature catalytic oxidation NO | |
| CN102861565A (en) | Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof | |
| CN106732581A (en) | A kind of Ru/CeTiO for low-temperature SCR reactionXThe preparation method of catalyst | |
| CN103769081A (en) | Room temperature nitric oxide adsorption/ catalytic oxidation catalyst and preparation method thereof | |
| CN105879879A (en) | High-sulfur-resistant ultralow-temperature SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof | |
| CN104772038A (en) | Method for purifying acrylonitrile apparatus absorbing tower tail gas by using Pd-CeO2/Me-beta molecular sieve | |
| CN114471522A (en) | High specific surface area anti-poisoning blast furnace gas hydrolysis catalyst and preparation method thereof | |
| CN102068994A (en) | Catalyst and preparation method thereof | |
| CN103043773A (en) | Catalytic wet oxidation method of flue gas desulfurization waste liquor | |
| CN104772037A (en) | Method for purifying acrylonitrile apparatus absorbing tower tail gas by using Pd-CeO2/Me-SAPO molecular sieve | |
| CN104785079A (en) | Method for purifying acrylonitrile device absorber off-gas by using CeMn/Me-SAPO molecular sieve | |
| CN114345355A (en) | Supported iron-based multi-component catalyst and preparation method thereof | |
| CN113578341A (en) | Synergistic NH3Preparation method of denitration catalyst with CO |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |