CN111686745B - Honeycomb type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof - Google Patents
Honeycomb type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 39
- 239000002071 nanotube Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 7
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 7
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 7
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 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 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
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- 230000008569 process Effects 0.000 abstract description 9
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- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 109
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 59
- 229910002091 carbon monoxide Inorganic materials 0.000 description 52
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 11
- 238000001354 calcination Methods 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 230000001413 cellular effect Effects 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
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- 238000005520 cutting process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
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- 235000019738 Limestone Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 239000010440 gypsum Substances 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
- B01D53/8646—Simultaneous elimination of the components
- B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
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- 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
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- 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
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/56—
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- 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)
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- 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
- B01J37/20—Sulfiding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The embodiment of the invention provides a honeycomb type CO and SO 2 And NO x A synchronous removal catalyst and a preparation method thereof. The catalyst carrier is gamma-Al 2 O 3 Nanotube with La as active component 0.7 Sr 0.3 Co x Fe 1‑x O 3 And preparing the perovskite into the honeycomb catalyst by adopting an extrusion forming process, and carrying out presulfurization treatment on the catalyst before use to prepare the final catalyst. The catalyst of the invention is prepared from gamma-Al 2 O 3 The nanotube is used as a carrier, so that the uniform distribution of active components is facilitated, the specific surface area of the catalyst can be greatly increased, and the catalyst has good catalytic activity and anti-poisoning performance within the range of 300-400 ℃; la 0.7 Sr 0.3 Co x Fe 1‑x O 3 The perovskite structure can realize CO and SO 2 And NO x Synchronously removing the three pollutants; the catalyst is pre-sulfurized to generate metal-sulfur bond pair CO for reducing SO 2 Has good catalytic activity, and the catalyst contains O 2 And H 2 The real smoke of O still has good reaction activity and selectivity; by adding the forming auxiliary agent, the preparation process is optimized, and the product has good warpEconomic benefit.
Description
Technical Field
The invention belongs to the field of environmental protectionThe technical field of denitration catalysis, in particular to honeycomb type CO and SO 2 And NO x The catalyst is synchronously removed, and the synchronous removal of CO, nitrogen and sulfur pollutants can be realized. The invention also provides the honeycomb type CO and SO 2 And NO x A preparation method of synchronous removal catalyst.
Background
Sulfur dioxide (SO) emitted from coal-fired power plants 2 ) And Nitrogen Oxides (NO) x ) Over 90% of the total emission, SO 2 And NO x Is an important atmospheric pollutant, can cause acid rain, photochemical smog, ozone layer damage and the like, and seriously harms the environment and human health. Currently, for effective treatment of SO 2 And NO x In order to avoid causing serious environmental pollution, the coal-fired power plant widely adopts an independent removal device to respectively carry out desulfurization and denitration treatment on discharged flue gas, wherein the desulfurization process mainly adopts a limestone gypsum wet process (FGD) mainstream denitration process as a Selective Catalytic Reduction (SCR), two independent devices respectively have ideal desulfurization efficiency and denitration efficiency, but the two devices are combined for desulfurization and denitration and have the defects of large occupied area, complex system, high investment and operation cost and the like, and synchronous SO removal is realized 2 And NO x The process is still in the research and development stage and is not widely applied.
In the existing synchronous desulfurization and denitrification process, carbon monoxide (CO) plays an important role. CO is a common component contained in the discharged flue gas and has reducibility, and SO is used as a reducing agent by utilizing CO existing in the flue gas 2 And NO x Reduction to elemental sulfur and N 2 Can realize SO 2 And NO x The simultaneous removal requires that the reaction be carried out in the presence of a catalyst, and therefore the development of a catalyst with high activity, selectivity and stability is the core of this process. Chinese patent document CN103464154A discloses a method for simultaneously catalyzing and reducing NO and SO by CO 2 The catalyst of (1), the catalyst being prepared from gamma-Al 2 O 3 Is a carrier, is loaded with metal oxide and can effectively reduce SO 2 And NO, but can not realize the removal of residual CO, so that the emission of the tail gas CO in the technical scheme exceeds the standard. Chinese patent document CN102049257A also discloses a catalyst for CO reduction and SO reduction 2 And NO, with TiO 2 -Al 2 O 3 The composite oxide is used as carrier, transition metal oxide is used as active component, and said catalyst can be presulfurized to obtain 98% SO at low temp. and high airspeed 2 Conversion and NO conversion close to 100%, but the use of this catalyst also does not allow the continued treatment of the remaining CO in the flue gas, which is emitted with the flue gas into the atmosphere, causing air pollution. In view of the above technical problems of the existing catalysts, it is urgently needed to develop a catalyst capable of realizing CO and SO 2 And NO x The catalyst is efficiently and synchronously removed.
Disclosure of Invention
The invention provides honeycomb type CO and SO, which aims to solve the technical problem that residual CO cannot be synchronously treated in the conventional synchronous desulfurization and denitrification process and provides a honeycomb type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof, and catalyst for reducing SO by CO 2 And NO x The reaction is highly active and oxidizes CO to CO 2 Also has high activity, and can efficiently realize CO and SO 2 And NO x And (4) synchronously removing.
To solve the above technical problems, embodiments of the present invention provide a cellular CO, SO 2 And NO x Synchronously removing a catalyst, wherein the catalyst is of a honeycomb structure and comprises 10-15% of La by mass 0.7 Sr 0.3 Co x Fe 1-x O 3 And 85 to 90% of gamma-Al 2 O 3 Nanotubes, said catalyst being presulfided.
Preferably, the La 0.7 Sr 0.3 Co x Fe 1-x O 3 Is of a perovskite structure, wherein x is 0.6-0.9.
Preferably, the gamma-Al 2 O 3 The length of the nano tube is 200-250 nm, and the outer diameter is 18-20 nm.
The embodiment of the invention also provides the cellular CO and SO 2 And NO x The preparation method of the synchronous removal catalyst comprises the following steps:
step 1, catalyst carrier preparation, namely, under the condition of stirring, alCl is added 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO 2 Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 45 ℃ for 12h, then carrying out reaction at 110 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to obtain the gamma-Al 2 O 3 A nanotube;
step 2, catalyst mud preparation, namely according to La 0.7 Sr 0.3 Co x Fe 1-x O 3 Respectively adding lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate into deionized water in proportion of the amount of lanthanum, strontium, cobalt and iron element substances, adding citric acid after completely dissolving, and stirring for 1-2 h at 40-60 ℃; adding the obtained solution into the gamma-Al prepared in the step 1 2 O 3 Adding kaolin, glass fiber, polyethylene oxide, polyacrylamide and hydroxypropyl methyl cellulose into the nano tube and stirring uniformly, and aging for 24-48 h under a closed condition to prepare catalyst mud;
step 3, preparing a honeycomb catalyst, comprising:
step 31, forming the honeycomb catalyst, namely forming the catalyst mud prepared in the step 2 by a vacuum extruder to obtain a wet blank of the honeycomb catalyst, drying the wet blank for 46 to 72 hours at the temperature of between 50 and 60 ℃ and at the humidity of between 80 and 90 percent, drying the wet blank for 36 to 48 hours at the temperature of between 70 and 90 ℃ and at the humidity of between 60 and 70 percent, drying the wet blank for 24 to 26 hours at the temperature of between 100 and 120 ℃, and roasting the wet blank for 4 to 10 hours at the temperature of between 700 and 750 ℃ to prepare the honeycomb catalyst;
step 32, pre-vulcanizing the catalyst, namely, pre-vulcanizing the honeycomb catalyst prepared in the step 31 in a process of preparing the catalyst by using CO and SO 2 、O 2 And N 2 Treating the pre-vulcanized gas at 180 ℃ for 1-4 h; then cut off SO 2 Gas and temperature rise to 350 ℃Keeping the temperature at 400 ℃ for 1 to 4 hours; finally heating to 600-700 ℃ and introducing SO 2 Keeping the gas for 2 to 6 hours to prepare the pre-vulcanized honeycomb La 0.7 Sr 0.3 Co x Fe 1-x O 3 /γ-Al 2 O 3 Catalyst is the honeycomb type CO and SO 2 And NO x And synchronously removing the catalyst.
Preferably, in step 1, the AlCl is adopted 3 The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl is added 3 And NaOH in a molar ratio of 1.
As the optimization of the step 1, the concentration of the hexadecyl trimethyl ammonium bromide solution is 0.3mol/L.
As a preference of step 2, the amount of the substance of citric acid added to the deionized water is equal to the total amount of the metal ion substance added.
Preferably, in step 2, the glass fiber has a length of 4 to 6mm.
Preferably, in step 2, the polyacrylamide is anionic and has a molecular weight of 200 to 400 ten thousand.
Preferably, in step 32, CO and SO in the pre-sulfiding gas 2 、O 2 And N 2 The volume ratio of each component is respectively 10%, 2%, 5% and 83%.
The technical scheme of the embodiment of the invention provides a novel gamma-Al 2 O 3 Nanotube as carrier, la 0.7 Sr 0.3 Co x Fe 1-x O 3 Perovskite is an active component, and the catalyst can synchronously remove CO and SO in flue gas through presulfurizing the treated catalyst 2 And NO x The beneficial effects are as follows:
1. with gamma-Al 2 O 3 The nanotube is used as a carrier, so that the uniform distribution of active components is facilitated, the specific surface area of the catalyst can be greatly increased, and the activity of the catalyst is effectively improved;
2. by appropriate selection of gamma-Al 2 O 3 The length and the outer diameter of the nano tube have larger specific surface table on the premise of ensuring the mechanical strength of the catalystArea;
3.γ-Al 2 O 3 the unique tube cavity structure of the nanotube can fix most active components inside the pipeline, and can effectively isolate solid toxic substances such as alkali metal, heavy metal and the like outside the pipeline, thereby avoiding the active components from being inactivated by the influence of the toxic substances in the flue gas and improving the anti-poisoning performance of the catalyst;
4.La 0.7 Sr 0.3 Co x Fe 1-x O 3 perovskite structure to SO 2 And NO x All have good reducibility and selectivity, simultaneously have good catalytic oxidation performance on CO, and can convert SO 2 Reduction to elemental sulfur, NO x Reduction to N 2 While oxidizing CO to CO 2 The synchronous removal of the three pollutants is realized;
5. after the catalyst is pre-vulcanized, the metal-sulfur bond in the Co-Fe-S structure can reduce SO to CO 2 Has good catalytic activity, and La generated after prevulcanization 2 O 2 S has double active centers, not only has the active center which reacts with CO to form intermediate product COS, but also promotes COS and SO 2 The active center of the reaction is adopted, no COS is generated in the product, and the selectivity of the reaction is high;
6. the catalyst is presulfided and then contains O 2 And H 2 The real smoke of O still has good reaction activity and selectivity, and has excellent anti-oxidation poisoning performance;
7. by adding various inorganic and organic forming aids, the preparation process is optimized, the honeycomb catalyst with high mechanical performance is prepared, the pressure drop is low, the service life is long, the investment and the operation cost are reduced, and the method has good economic benefit.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
The invention aims at the existing problems and provides cellular CO and SO 2 And NO x Synchronous removal of catalyst, which can efficiently realize CO and SO 2 And NO x And (4) synchronously removing.
In order to implement the above technical solution, an embodiment of the present invention provides a cellular CO and SO 2 And NO x Synchronously removing the catalyst, wherein the catalyst is of a honeycomb structure and comprises 10-15% of La by mass 0.7 Sr 0.3 Co x Fe 1-x O 3 And 85 to 90% of gamma-Al 2 O 3 Nanotubes and catalyst are presulfurized. As a more preferred embodiment, la 0.7 Sr 0.3 Co x Fe 1-x O 3 Selecting a perovskite structure, wherein x is 0.6-0.9; gamma-Al 2 O 3 The length of the nano tube can be selectively controlled to be 200-250 nm, the external diameter size is controlled to be 18-20 nm, and the gamma-Al can be ensured 2 O 3 The nanotube as catalyst carrier has relatively great specific surface area and no reduction in the mechanical strength of the catalyst.
In order to better realize the technical scheme, the invention also provides the cellular CO and SO 2 And NO x The preparation method of the synchronous removal catalyst comprises the following steps:
s1, catalyst carrier preparation, namely, under the stirring condition, preparing AlCl 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO 2 Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 45 ℃ for 12h, then carrying out reaction at 110 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to obtain the gamma-Al 2 O 3 A nanotube;
s2, preparing catalyst mud, namely according to La 0.7 Sr 0.3 Co x Fe 1-x O 3 Respectively adding lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate into deionized water according to the mass proportion of lanthanum, strontium, cobalt and iron elements, and adding citric acid after completely dissolvingStirring for 1-2 h at 40-60 ℃; adding the obtained solution to the gamma-Al prepared in the step S1 2 O 3 Adding kaolin, glass fiber, polyethylene oxide, polyacrylamide and hydroxypropyl methyl cellulose into the nano tube and stirring uniformly, and aging for 24-48 h under a closed condition to prepare catalyst mud;
s3, preparing a honeycomb catalyst, which comprises the following steps:
s31, forming a honeycomb catalyst, namely forming the catalyst mud prepared in the step S2 by using a vacuum extruder to obtain a honeycomb catalyst wet blank, drying for 46-72 h at the temperature of 50-60 ℃ and the humidity of 80-90%, drying for 36-48 h at the temperature of 70-90 ℃ and the humidity of 60-70%, drying for 24-26 h at the temperature of 100-120 ℃, and roasting for 4-10 h at the temperature of 700-750 ℃ to prepare the honeycomb catalyst;
s32, presulfurizing the catalyst, namely, the honeycomb catalyst prepared in the step S31 is prepared by CO and SO 2 、 O 2 And N 2 Treating the pre-vulcanized gas at 180 ℃ for 1-4 h; then cut off SO 2 Heating the gas to 350-400 ℃ and keeping the temperature for 1-4 h; finally heating to 600-700 ℃ and introducing SO 2 Keeping the gas for 2 to 6 hours to prepare the pre-vulcanized honeycomb La 0.7 Sr 0.3 Co x Fe 1-x O 3 /γ-Al 2 O 3 Catalyst, i.e. said honeycomb type CO, SO 2 And NO x And synchronously removing the catalyst.
As a more preferred embodiment:
in step S1, alCl 3 The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl 3 And NaOH in a molar ratio of 1; the concentration of the hexadecyl trimethyl ammonium bromide solution is 0.3mol/L;
in the step S2, the amount of the citric acid substances added into the deionized water is equal to the total amount of the added metal ion substances; the length of the glass fiber is 4-6 mm; the polyacrylamide is anionic, and the molecular weight is 200-400 ten thousand.
In step S32, CO and SO in the pre-sulfidation gas 2 、O 2 And N 2 Each ingredient isThe volume ratio is respectively 10%, 2%, 5% and 83%.
The technical solution of the present invention is specifically described below by specific examples:
example 1
Honeycomb CO and SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
Respectively dissolving 6.544kg of AlCl in 98L of deionized water 3 24.5L of deionized water was dissolved in 3.922kg of NaOH, and then AlCl was prepared under stirring 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 45 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 45 ℃ for 12h, and then carrying out reaction at 110 ℃ for 12h; washing the obtained product with water, filtering, drying in air at 80 deg.C for 24 hr, calcining in air at 500 deg.C for 24 hr, and collecting 2387g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
269.15g of La (NO) are taken 3 ) 3 6H 2 O, 56.38g Sr (NO) 3 ) 2 155.06g of Co (NO) 3 ) 2 6H 2 O and 143.50g Fe (NO) 3 ) 3 9H 2 Dissolving O in 1.2L of water, adding 341.22g of citric acid, and stirring at 40 ℃ for 1h; the prepared solution was added to 1800g of gamma-Al 2 O 3 And adding kaolin, 4mm glass fiber, polyethylene oxide, polyacrylamide and hydroxypropyl methyl cellulose into the carrier, and aging for 24 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Forming the catalyst mud into a honeycomb catalyst wet blank body by a vacuum extruder, drying for 72 hours at the temperature of 50 ℃ and the humidity of 80%, and then drying at the temperature of 70 ℃ and the humidity of 60%Drying at 120 deg.C for 48h, drying at 120 deg.C for 26h, and calcining at 700 deg.C for 10h to obtain La content of 10% 0.7 Sr 0.3 Co 0.6 Fe 0.4 O 3 /90％γ-Al 2 O 3 A honeycomb catalyst with mass percent.
The prepared honeycomb catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO 2 5% of O 2 And 83% of N 2 Treating the pre-vulcanized gas for 4 hours at 180 ℃; then cutting off SO 2 Heating the gas to 400 ℃, and keeping the temperature for 1h; finally, the temperature is raised to 700 ℃, and SO is introduced 2 Keeping the gas for 6 hours to obtain the pre-vulcanized honeycomb catalyst.
The prepared catalyst component is La accounting for 10 percent by mass 0.7 Sr 0.3 Co 0.6 Fe 0.4 O 3 /90％γ-Al 2 O 3 。
Example 2
Another cellular CO, SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
7.853kg of AlCl were dissolved in 117.6L of deionized water, respectively 3 29.4L of deionized water was dissolved in 4.706kg of NaOH, and then the prepared AlCl was stirred 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 45 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 45 ℃ for 12h, and then carrying out reaction at 110 ℃ for 12h; washing the obtained product with water, filtering, drying in air at 120 deg.C for 12h, calcining in air at 550 deg.C for 4h, and collecting 2876g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
625.30g of La (NO) are taken 3 ) 3 6H 2 O, 130.98g of Sr (NO) 3 ) 2 540.36g of Co (NO) 3 ) 2 6H 2 O and 83.34g Fe (NO) 3 ) 3 9H 2 Dissolving O in 1.9L water, adding 792.73g citric acid, and stirring at 60 deg.C for 2h; 2550g of gamma-Al were added to the prepared solution 2 O 3 And adding kaolin, 6mm glass fiber, polyethylene oxide, polyacrylamide and hydroxypropyl methyl cellulose into the carrier, and aging for 48 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Forming the catalyst mud into a honeycomb catalyst wet blank body by a vacuum extruder, drying for 46h at the temperature of 60 ℃ and the humidity of 90%, drying for 36h at the temperature of 90 ℃ and the humidity of 70%, drying for 24h at the temperature of 100 ℃, and finally roasting for 4h at the temperature of 750 ℃ to obtain the catalyst mud with the La content of 15% 0.7 Sr 0.3 Co 0.9 Fe 0.1 O 3 /85％γ-Al 2 O 3 A honeycomb catalyst with mass percent.
The prepared honeycomb catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO 2 5% of O 2 And 83% of N 2 Treating the mixture for 1h at 180 ℃ in the formed prevulcanization gas; then cutting off SO 2 Heating the gas to 350 ℃, and keeping the temperature for 4 hours; finally heating to 600 ℃, and introducing SO 2 Keeping the gas for 2 hours to obtain the pre-vulcanized honeycomb catalyst.
The prepared catalyst component is La accounting for 15 percent by mass 0.7 Sr 0.3 Co 0.9 Fe 0.1 O 3 /85％γ-Al 2 O 3 。
Example 3
Another honeycomb type CO and SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
9.162kg of AlCl were dissolved in 137.3L of deionized water, respectively 3 34.3L of deionized water was dissolved in 5.490kg of NaOH, and then the prepared AlCl was stirred 3 The solution is slowly dripped into NaOH solution to obtain transparencyNaAlO (R) of 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 45 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 45 ℃ for 12h, and then carrying out reaction at 110 ℃ for 12h; washing the obtained product with water, filtering, drying in air at 100 deg.C for 16h, calcining in air at 500 deg.C for 5h, and collecting 3397g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
484.35g of La (NO) was taken 3 ) 3 6H 2 O, 101.46g of Sr (NO) 3 ) 2 348.80g of Co (NO) 3 ) 2 6H 2 O and 161.39g Fe (NO) 3 ) 3 9H 2 Dissolving O in 2.0L of water, adding 614.05g of citric acid, and stirring at 50 ℃ for 1h; 2640g of gamma-Al was added to the solution 2 O 3 And adding kaolin, 5mm glass fiber, polyethylene oxide, polyacrylamide and hydroxypropyl methyl cellulose into the carrier, and aging for 36 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Forming the catalyst mud into honeycomb catalyst wet blank by vacuum extruder, drying at 55 deg.C and 80% for 48 hr, drying at 80 deg.C and 60% for 40 hr, drying at 105 deg.C for 24 hr, and calcining at 700 deg.C for 8 hr to obtain 12% La 0.7 Sr 0.3 Co 0.75 Fe 0.25 O 3 /88％γ-Al 2 O 3 A honeycomb catalyst of the components by mass percent.
The prepared honeycomb catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO 2 5% of O 2 And 83% of N 2 Treating the pre-vulcanized gas for 2 hours at 180 ℃; then cutting off SO 2 Heating the gas to 400 ℃, and keeping the temperature for 3 hours; finally heating to 650 ℃, and introducing SO 2 Gas, hold for 4h, 12% La to obtain prevulcanization 0.7 Sr 0.3 Co 0.75 Fe 0.25 O 3 /88％γ-Al 2 O 3 A honeycomb catalyst.
The prepared catalyst component is 12 percent by mass of La 0.7 Sr 0.3 Co 0.75 Fe 0.25 O 3 /88％γ-Al 2 O 3 。
Example 4
Another honeycomb type CO and SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
Respectively dissolving 10.471kg of AlCl in 156.9L of deionized water 3 39.2L of deionized water was dissolved in 6.274kg of NaOH and the prepared AlCl was stirred 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 45 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 45 ℃ for 12h, and then carrying out reaction at 110 ℃ for 12h; washing the obtained product with water, filtering, drying in air at 90 deg.C for 16h, calcining in air at 525 deg.C for 6h, and collecting 3905g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
538.31g of La (NO) was taken 3 ) 3 6H 2 O, 112.76g of Sr (NO) 3 ) 2 341.13g of Co (NO) 3 ) 2 6H 2 O and 243.95g Fe (NO) 3 ) 3 9H 2 Dissolving O in 2.8L of water, adding 682.45g of citric acid, and stirring at 40 ℃ for 2 hours; 3600g of gamma-Al is added into the prepared solution 2 O 3 And adding kaolin, 4mm glass fiber, polyethylene oxide, polyacrylamide and hydroxypropyl methyl cellulose into the carrier, and aging for 36 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
The catalyst mud is formed by a vacuum extruderDrying the green honeycomb catalyst at 50 deg.C and 80% humidity for 50 hr, drying at 75 deg.C and 60% humidity for 36 hr, drying at 120 deg.C for 26 hr, and calcining at 710 deg.C for 5 hr to obtain 10% La cell 0.7 Sr 0.3 Co 0.66 Fe 0.34 O 3 /90％γ-Al 2 O 3 A honeycomb catalyst with mass percent.
The honeycomb catalyst is prepared by mixing 10% of CO and 2% of SO by volume percentage 2 5% of O 2 And 83% of N 2 Treating the pre-vulcanized gas at 180 ℃ for 2.5 hours; then cutting off SO 2 Heating the gas to 400 ℃, and keeping the temperature for 1.5h; finally, the temperature is raised to 675 ℃, and SO is introduced 2 Gas, hold for 3.5h, 10% La of pre-vulcanized 0.7 Sr 0.3 Co 0.66 Fe 0.34 O 3 /90％γ-Al 2 O 3 A honeycomb catalyst.
The obtained catalyst component is La by mass percentage of 10% 0.7 Sr 0.3 Co 0.66 Fe 0.34 O 3 /90％γ-Al 2 O 3 。
The catalysts prepared in the previous examples 1 to 4 were subjected to CO and SO at 300 ℃ and 400 ℃ respectively 2 And NO x Synchronous removal test, the test working condition is: CO concentration 500mg/m 3 NO concentration 420mg/m 3 ，SO 2 The concentration is 450mg/m 3 ，O 2 Volume ratio of 5%, H 2 The volume ratio of O is 5 percent, and the space velocity is 4500h -1 . The efficiency data from the removal test are given in the following table:
TABLE 1.300 ℃ CO, SO 2 And NO x Synchronous stripping efficiency
TABLE 2.400 ℃ CO, SO 2 And NO x Synchronous stripping efficiency
As can be seen from the above tables 1 and 2, the catalyst provided by the embodiments of the present invention has good catalytic activity and anti-oxygen poisoning performance at a temperature of 300-400 ℃, and can realize CO and SO 2 And NO x High-efficiency synchronous removal.
It should be understood that the above-mentioned embodiments are only for illustrating the technical concept and features of the present invention, and are not intended to be exhaustive or to limit the scope of the present invention, for providing those skilled in the art with understanding the present invention and implementing the same. Modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is set forth in the following claims.
Claims (6)
1. Honeycomb CO and SO 2 And NO x The preparation method of the synchronous removal catalyst is characterized by comprising the following steps:
step 1. Catalyst support preparation, comprising:
under the condition of stirring, adding AlCl 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO 2 Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 45 ℃ for 12h, then carrying out reaction at 110 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to obtain the gamma-Al 2 O 3 A nanotube;
step 2, catalyst mud preparation, comprising:
according to La 0.7 Sr 0.3 Co x Fe 1-x O 3 Respectively adding lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate into deionized water according to the proportion of the lanthanum, strontium, cobalt and ferric element substances, and adding lemon after completely dissolvingStirring citric acid at 40-60 ℃ for 1-2 h; adding the obtained solution into the gamma-Al prepared in the step 1 2 O 3 Adding kaolin, glass fiber, polyethylene oxide, polyacrylamide and hydroxypropyl methyl cellulose into the nano tube and stirring uniformly, and aging for 24-48 h under a closed condition to prepare catalyst mud;
step 3, preparing a honeycomb catalyst, which comprises the following steps:
step 31. Honeycomb catalyst molding, comprising:
forming the catalyst mud material prepared in the step 2 by a vacuum extruder to obtain a honeycomb type catalyst wet blank, drying for 46-72 h at 50-60 ℃ and humidity of 80-90%, drying for 36-48 h at 70-90 ℃ and humidity of 60-70%, drying for 24-26 h at 100-120 ℃, and roasting for 4-10 h at 700-750 ℃ to prepare the honeycomb type catalyst;
step 32. Catalyst presulfiding, comprising:
the honeycomb catalyst prepared in the step 31 is prepared by reacting CO and SO 2 、O 2 And N 2 Treating the pre-vulcanized gas at 180 ℃ for 1-4 h; then cut off SO 2 Heating the gas to 350-400 ℃ and keeping the temperature for 1-4 h; finally heating to 600-700 ℃ and introducing SO 2 Keeping the gas for 2 to 6 hours to prepare the pre-vulcanized honeycomb La 0.7 Sr 0.3 Co x Fe 1-x O 3 /γ-Al 2 O 3 Catalyst, i.e. said honeycomb type CO, SO 2 And NO x Synchronously removing the catalyst; the catalyst is of a honeycomb structure and comprises 10-15% of La by mass 0.7 Sr 0.3 Co x Fe 1-x O 3 And 85 to 90 percent of gamma-Al 2 O 3 Nanotubes, said catalyst being presulfided; the La 0.7 Sr 0.3 Co x Fe 1-x O 3 Is of a perovskite structure, wherein x is 0.6 to 0.9; the gamma-Al 2 O 3 The length of the nano tube is 200-250 nm, and the outer diameter is 18-20 nm.
2. According to claimThe method of claim 1, wherein AlCl is added in step 1 3 The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl 3 And NaOH in a molar ratio of 1.
3. The method according to claim 1, wherein the concentration of the cetyltrimethylammonium bromide solution in the step 1 is 0.3mol/L.
4. The method according to claim 1, wherein the amount of the citric acid added to the deionized water in the step 2 is equal to the total amount of the metal ion species added.
5. The method as claimed in claim 1, wherein the length of the glass fiber in the step 2 is 4 to 6mm.
6. The method of claim 1, wherein the pre-sulfiding gas in step 32 is CO, SO 2 、O 2 And N 2 The volume ratio of each component is respectively 10%, 2%, 5% and 83%.
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