CN109731569B - Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof - Google Patents
Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000011148 porous material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 29
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 11
- 229920000742 Cotton Polymers 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 11
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 11
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 11
- 239000004310 lactic acid Substances 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 9
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000002149 hierarchical pore Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/60—
-
- 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
- B01J37/08—Heat treatment
Abstract
The invention discloses a honeycomb type SCR denitration catalyst with a three-dimensional multi-stage pore channel structure, which is prepared from the following raw materials in parts by weight: 80-100 parts of titanium dioxide, 1-2 parts of pulp cotton, 0.1-0.5 part of multi-walled carbon nano tube, 0.5-2.5 parts of carbon black, 1-3 parts of silicon dioxide, 5-10 parts of glass fiber, 1-3 parts of ammonium metavanadate, 5-10 parts of ammonium metatungstate, 5-10 parts of cerium nitrate hexahydrate, 5-15 parts of monoethanolamine, 1-2 parts of carboxymethyl cellulose, 1-2 parts of ethylene oxide, 5-15 parts of lactic acid, 1-2 parts of stearic acid, 15-25 parts of ammonia water and 30-50 parts of deionized water. The invention also discloses a method for preparing the honeycomb SCR denitration catalyst with the three-dimensional multi-stage pore channel structure, and the prepared catalyst has a three-dimensional orderly interconnected pore network and mesoporous structure, so that the compressive strength is improved, and the characteristic of large specific surface area is maintained.
Description
Technical Field
The invention belongs to the technical field of industrial denitration, and particularly relates to a honeycomb type SCR denitration catalyst with a three-dimensional multi-stage pore channel structure and a preparation method thereof.
Background
As a dry denitration technique for removing nitrogen oxides from coal-fired flue gas, a selective catalytic reduction denitration method is widely used, which uses ammonia as a reducing agent to make NO and NO in the flue gas2Post-reduction through catalyst layerGenerating N2And H2O to remove NO in the flue gasxThe purpose of (1). The catalyst is mostly TiO2As a carrier, V2O5、WO3The porous medium which is an active component has the advantages of high denitration rate, good selectivity, stable operation, moderate temperature and the like, so the porous medium is favored by researchers at home and abroad. The core problem lies in the development, development and improvement of the catalyst.
At present, a denitration arrangement mode of a coal-fired power plant mainly adopts a high-dust arrangement mode, and the passing flue gas has large dust, so that a catalyst bed layer is easy to block to generate high pressure; in addition, the catalyst is consumed by loading, impact, abrasion of particulate matters in smoke and the like in the using process, so that in practical application, in addition to ensuring the activity of the catalyst, the practicability of the catalyst, such as mechanical strength, porosity and other properties, is more important to consider. In the active temperature range of the catalyst, the denitration efficiency is increased along with the increase of the specific surface area, and the increase of the porosity of the catalyst can improve the specific surface area to a certain extent. However, it is difficult to prepare a high strength catalyst under high porosity conditions. Therefore, how to prepare a honeycomb denitration catalyst with high porosity and certain mechanical strength is still a problem to be solved urgently.
The forming process of the honeycomb denitration catalyst and the use of the pore-forming agent directly influence the mechanical strength and the porosity of the honeycomb denitration catalyst, so the forming process needs to be optimized. At present, some researchers can prepare the honeycomb denitration catalyst with high porosity and a hierarchical pore structure by adjusting extrusion pressure and the addition amount and the type of a pore-forming agent, so that the mechanical strength is improved, and the using amount of the catalyst can be reduced. Therefore, it is an effective method to control the mechanical strength and denitration efficiency of the catalyst by adjusting the pore structure.
Adsorption capacity of catalyst for removing NOxThe efficiency of adsorption has a tremendous impact, and the most direct factor associated with adsorption capacity is the microstructure of the catalyst. A good microstructure means that the catalyst has larger specific surface area, more micropore structures, proper pore size distribution and rapid mass transfer rate, and the gas distribution of the catalyst is increasedThe adsorption capacity of the catalyst is increased, and the denitration performance is improved. However, when the specific surface area is increased, the number of micropores in the catalyst increases, and the average pore diameter decreases, which is disadvantageous for the diffusion of gas in the catalyst. Therefore, the influence of the pore structure of the catalyst on the denitration process depends on the degree of influence on the gas diffusion and the chemical reaction process, respectively, when the pore structure is changed. The three-dimensional multi-stage pore channel structure can greatly increase the specific surface area of the material and the utilization rate of pores, and the effect of enhancing the diffusion rate of gas in pores and enhancing the denitration effect is achieved. The material with the multi-stage pore canal structure can also reduce pore canal blockage caused by macromolecules and improve the diffusion efficiency, the mesoporous or microporous pore canals are used as the reaction space of reactants, the reactants can quickly approach an active site in a macroporous system with small pressure drop, and meanwhile, products can be timely separated to stop the reaction. At present, the research of introducing a three-dimensional multilevel pore channel structure into a honeycomb denitration catalyst is not reported in documents and patents.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to regulate and control the macroscopic performance of the honeycomb type denitration catalyst by modifying the microscopic pore structure and the pore characteristics of the honeycomb type denitration catalyst so as to prepare the honeycomb type denitration catalyst with high porosity and certain mechanical strength.
The invention adopts the following technical scheme to solve the technical problems:
the honeycomb type SCR denitration catalyst with the three-dimensional multi-stage pore structure comprises the following raw materials in parts by weight: 80-100 parts of titanium dioxide, 1-2 parts of pulp cotton, 0.1-0.5 part of multi-walled carbon nano tube, 0.5-2.5 parts of carbon black, 1-3 parts of silicon dioxide, 5-10 parts of glass fiber, 1-3 parts of ammonium metavanadate, 5-10 parts of ammonium metatungstate, 5-10 parts of cerium nitrate hexahydrate, 5-15 parts of monoethanolamine, 1-2 parts of carboxymethyl cellulose, 1-2 parts of ethylene oxide, 5-15 parts of lactic acid, 1-2 parts of stearic acid, 15-25 parts of ammonia water and 30-50 parts of deionized water.
Preferably, the method for preparing the honeycomb type SCR denitration catalyst with the three-dimensional multi-stage pore channel structure comprises the following steps:
(1) dispersing the multi-walled carbon nanotube and carbon black in mixed acid, acidizing for 3-6 h, cooling to room temperature, diluting with distilled water, filtering and washing to be neutral, drying the product at 75-80 ℃ for 10-12 h in vacuum, and grinding into powder to obtain acidified multi-walled carbon nanotube and carbon black mixture powder;
(2) adding the acidified multi-walled carbon nanotube and carbon black mixture powder obtained in the step (1) into ammonia water, and uniformly dispersing by ultrasonic to obtain a mixed solution I;
(3) adding ammonium metavanadate, ammonium metatungstate and cerous nitrate hexahydrate into a mixed solution of monoethanolamine and deionized water, and heating and dissolving to obtain a mixed solution II;
(4) adding the mixed solution I and the mixed solution II into a mixture containing titanium dioxide, silicon dioxide, glass fiber, stearic acid and pulp cotton under stirring, mixing, adding carboxymethyl cellulose, ethylene oxide and lactic acid, mixing again to obtain mixed pug, and aging;
(5) and (4) extruding, molding, drying and calcining the mixed pug obtained in the step (4) to obtain a target product.
Preferably, the diameter of the multi-walled carbon nanotube in the step (1) is 10-20 nm, and the length is 5-15 μm; the particle size of the carbon black is about 15-20 nm.
Preferably, the mass ratio of the multi-walled carbon nanotubes to the carbon black in the step (1) is 1: 1-5; the mass ratio of the total mass of the multi-wall carbon nano tubes and the carbon black to the mixed acid solution is 1: 5-10.
Preferably, the mixed acid is formed by mixing concentrated sulfuric acid and concentrated nitric acid according to the volume ratio of 3: 1.
Preferably, the concentration of the ammonia water in the step (2) is 15%, the ultrasonic dispersion power is 400-800W, and the time is 0.5-2 h.
Preferably, the heating and dissolving temperature in the step (3) is 60-90 ℃.
Preferably, the mixture in the step (4) is stirred for 0.5-1 h before being added into the mixed solution I and the mixed solution II.
Preferably, in the step (4), the mixed solution I and the mixed solution II are added into the mixture containing titanium dioxide, silicon dioxide, glass fiber, stearic acid and pulp cotton under the stirring of the rotation speed of 200-400 rpm, the mixture is mixed at the rotation speed of 600-800 rpm, after the uniform mixing, carboxymethyl cellulose, ethylene oxide and lactic acid are added at 70-90 ℃, the mixture is mixed again at the rotation speed of 600-800 rpm, mixed pug is obtained, and the aging is carried out for 12-48 h.
Preferably, the number of the honeycomb catalyst holes extruded in the step (5) is 20 × 20 holes; the drying temperature is 20-60 ℃; and introducing mixed gas with the oxygen content of 30-50% in the calcining process, and keeping the whole calcining under the oxygen-enriched condition.
The invention has the following beneficial effects: the invention discloses a honeycomb SCR denitration catalyst with a three-dimensional multistage pore channel structure and a preparation method thereof.
In the preparation process, the multi-wall carbon nano-tubes and the carbon black are acidified to improve the water solubility, so that the multi-wall carbon nano-tubes and the carbon black are uniformly dispersed in pug, the one-dimensional carbon nano-tubes form a net-shaped interweaving structure, and are fully calcined, oxidized and decomposed under the oxygen-rich condition, and all micropores and mesopores are connected to form a three-dimensional multi-stage channel with rapid mass transfer. The three-dimensional pore channel structure has rich space network-shaped nano-scale micro-pores-mesopores and slender mass transfer channels, so that the porosity and the specific surface area of the catalyst can be improved, and higher crushing strength is kept; in addition, the characteristic that pore channels are communicated with each other can resist the uneven deposition of vanadium oxide and dust on the surface of flue gas and slow down the coverage of active sites caused by the blockage of calcium sulfate and other particles on micropores. The prepared catalyst has high porosity, certain mechanical strength and good industrial application prospect.
Detailed Description
In order to facilitate the understanding of the technical solutions of the present invention for those skilled in the art, the technical solutions of the present invention will now be further described with reference to the embodiments. The described embodiments are only some, but not all embodiments of the invention.
Example 1
A preparation method of a honeycomb type SCR denitration catalyst with a three-dimensional multi-stage pore channel structure comprises the following steps:
(1) dispersing 0.2kg of multi-walled carbon nano-tube and 1.0kg of carbon black in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the total mass of 8kg, stirring at 40 ℃ for 3h, cooling to room temperature, diluting with distilled water, filtering and washing to be neutral, vacuum-drying the product at 75 ℃ for 10h, and grinding into powder to obtain acidified mixture powder of the multi-walled carbon nano-tube and the carbon black; wherein the volume ratio of V (concentrated sulfuric acid) to V (concentrated nitric acid) in the mixed acid solution is 3: 1;
(2) adding the obtained acidified multi-walled carbon nanotube and carbon black mixture powder into 20kg of 15% ammonia water, and performing ultrasonic dispersion for 0.5h under the power of 400W to obtain a mixed solution I;
(3) sequentially adding 1.5kg of ammonium metavanadate, 6kg of ammonium metatungstate and 6kg of cerous nitrate hexahydrate into an aqueous solution containing 5kg of monoethanolamine, heating to 60 ℃ and fully dissolving to obtain a mixed solution II;
(4) adding the mixed solution I and the mixed solution II into a mixture containing 90kg of titanium dioxide, 2kg of silicon dioxide, 6kg of glass fiber, 2kg of stearic acid and 1.5kg of pulp cotton under the stirring of the rotation speed of 200rpm, mixing at the rotation speed of 600rpm, adding 8kg of lactic acid, 1.5kg of carboxymethyl cellulose and 1.5kg of ethylene oxide at 70 ℃ after uniformly mixing, mixing again at the rotation speed of 600rpm to obtain mixed pug, and aging for 12 hours;
(5) extruding and molding the catalyst mixed pug obtained in the step (4) by using a 20X 20 grinding tool, drying at 20 ℃ until the moisture is lower than 3%, and calcining at 550 ℃ for 5 hours in an atmosphere with 35% of oxygen content to obtain a target product;
cutting the obtained catalyst monomer into test blocks of 150mm multiplied by 150mm, testing the mechanical strength by using an electronic universal testing machine, and testing the specific surface area by using a static nitrogen adsorption method; according to the specific implementation steps of the example 1, the crushing strength of the prepared product is respectively up to 1.5MPa and 4.9MPa in the radial/axial direction, and the specific surface area is up to 68m2/g。
Example 2
A preparation method of a honeycomb type SCR denitration catalyst with a three-dimensional multi-stage pore channel structure comprises the following steps:
(1) dispersing 0.3kg of multi-walled carbon nano-tube and 1.5kg of carbon black in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the total mass of 10kg, stirring at 40 ℃ for 4h, cooling to room temperature, diluting with distilled water, filtering and washing to be neutral, vacuum-drying the product at 80 ℃ for 12h, and grinding into powder to obtain acidified mixture powder of the multi-walled carbon nano-tube and the carbon black; wherein the volume ratio of V (concentrated sulfuric acid) to V (concentrated nitric acid) in the mixed acid solution is 3: 1;
(2) adding the obtained acidified multi-walled carbon nanotube and carbon black mixture powder into 20kg of 15% ammonia water, and performing ultrasonic dispersion for 1h under the power of 600W to obtain a mixed solution I;
(3) sequentially adding 1.5kg of ammonium metavanadate, 6kg of ammonium metatungstate and 6kg of cerous nitrate hexahydrate into an aqueous solution containing 5kg of monoethanolamine, heating to 80 ℃ and fully dissolving to obtain a mixed solution II;
(4) adding the mixed solution I and the mixed solution II into a mixture containing 90kg of titanium dioxide, 2kg of silicon dioxide, 6kg of glass fiber, 2kg of stearic acid and 1.8kg of pulp cotton under the stirring of the rotation speed of 300rpm, mixing at the rotation speed of 700rpm, adding 8kg of lactic acid, 1.5kg of carboxymethyl cellulose and 1.5kg of ethylene oxide at the temperature of 80 ℃ after uniform mixing, mixing again at the rotation speed of 700rpm to obtain mixed pug, and aging for 24 hours;
(5) extruding and molding the catalyst mixed pug obtained in the step (4) by using a 20X 20 grinding tool, drying at 40 ℃ until the moisture is lower than 3%, and calcining at 550 ℃ for 5 hours in an atmosphere containing 40% of oxygen to obtain a target product;
the obtained catalyst monomer was cut into test pieces of 150mm × 150mm × 150mm, the mechanical strength was measured using an electronic universal tester, and the specific surface area was measured using a static nitrogen adsorption method. According to the specific implementation steps of the embodiment 2, the crushing strength of the prepared product is respectively up to 1.1MPa and 4.1MPa in the radial/axial direction, and the specific surface area is up to 72m2/g。
Example 3
A preparation method of a honeycomb type SCR denitration catalyst with a three-dimensional multi-stage pore channel structure comprises the following steps:
(1) dispersing 0.1kg of multi-walled carbon nano-tube and 0.5kg of carbon black in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid with the total mass of 6kg, stirring at 40 ℃ for 6h, cooling to room temperature, diluting with distilled water, filtering and washing to be neutral, vacuum-drying the product at 80 ℃ for 12h, and grinding into powder to obtain acidified mixture powder of the multi-walled carbon nano-tube and the carbon black; wherein the volume ratio of V (concentrated sulfuric acid) to V (concentrated nitric acid) in the mixed acid solution is 3: 1;
(2) adding the obtained acidified multi-walled carbon nanotube and carbon black mixture powder into 20kg of 15% ammonia water, and performing ultrasonic dispersion for 2 hours at the power of 800W to obtain a mixed solution I;
(3) sequentially adding 1.5kg of ammonium metavanadate, 6kg of ammonium metatungstate and 6kg of cerous nitrate hexahydrate into an aqueous solution containing 5kg of monoethanolamine, heating to 90 ℃ and fully dissolving to obtain a mixed solution II;
(4) adding the mixed solution I and the mixed solution II into a mixture containing 90kg of titanium dioxide, 2kg of silicon dioxide, 6kg of glass fiber, 2kg of stearic acid and 1.0kg of pulp cotton under the stirring of 400rpm, mixing at 800rpm, adding 8kg of lactic acid, 1.5kg of carboxymethyl cellulose and 1.5kg of ethylene oxide at 90 ℃ after uniform mixing, mixing again at 800rpm to obtain mixed pug, and aging for 24 hours;
(5) extruding and molding the catalyst mixed pug obtained in the step (4) by using a 20X 20 grinding tool, drying at 60 ℃ until the moisture is lower than 3%, and calcining at 550 ℃ for 5 hours in an atmosphere with 30% of oxygen content to obtain a target product;
the obtained catalyst monomer was cut into test pieces of 150mm × 150mm × 150mm, the mechanical strength was measured using an electronic universal tester, and the specific surface area was measured using a static nitrogen adsorption method. According to the specific implementation steps of the embodiment 3, the crushing strength of the prepared product is respectively up to 1.7MPa and 5.3MPa in the radial/axial direction, and the specific surface area is up to 51m2/g。
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. The honeycomb type SCR denitration catalyst with a three-dimensional multi-stage pore channel structure is characterized by comprising the following raw materials in parts by weight: 80-100 parts of titanium dioxide, 1-2 parts of pulp cotton, 0.1-0.5 part of multi-walled carbon nano tube, 0.5-2.5 parts of carbon black, 1-3 parts of silicon dioxide, 5-10 parts of glass fiber, 1-3 parts of ammonium metavanadate, 5-10 parts of ammonium metatungstate, 5-10 parts of cerium nitrate hexahydrate, 5-15 parts of monoethanolamine, 1-2 parts of carboxymethyl cellulose, 1-2 parts of ethylene oxide, 5-15 parts of lactic acid, 1-2 parts of stearic acid, 15-25 parts of ammonia water and 30-50 parts of deionized water;
the method for preparing the honeycomb type SCR denitration catalyst with the three-dimensional multi-stage pore channel structure comprises the following steps:
(1) dispersing the multi-walled carbon nanotube and carbon black in mixed acid, acidizing for 3-6 h, cooling to room temperature, diluting with distilled water, filtering and washing to be neutral, drying the product at 75-80 ℃ for 10-12 h in vacuum, and grinding into powder to obtain acidified multi-walled carbon nanotube and carbon black mixture powder;
(2) adding the acidified multi-walled carbon nanotube and carbon black mixture powder obtained in the step (1) into ammonia water, and uniformly dispersing by ultrasonic to obtain a mixed solution I;
(3) adding ammonium metavanadate, ammonium metatungstate and cerous nitrate hexahydrate into a mixed solution of monoethanolamine and deionized water, and heating and dissolving to obtain a mixed solution II;
(4) adding the mixed solution I and the mixed solution II into a mixture containing titanium dioxide, silicon dioxide, glass fiber, stearic acid and pulp cotton under stirring, mixing, adding carboxymethyl cellulose, ethylene oxide and lactic acid, mixing again to obtain mixed pug, and aging;
(5) extruding, molding, drying and calcining the mixed pug obtained in the step (4) to obtain a target product;
and introducing mixed gas with the oxygen content of 30-50% in the calcining process, and keeping the whole calcining under the oxygen-enriched condition.
2. A method for preparing the honeycomb SCR denitration catalyst having a three-dimensional multi-stage pore channel structure according to claim 1, comprising the steps of:
(1) dispersing the multi-walled carbon nanotube and carbon black in mixed acid, acidizing for 3-6 h, cooling to room temperature, diluting with distilled water, filtering and washing to be neutral, drying the product at 75-80 ℃ for 10-12 h in vacuum, and grinding into powder to obtain acidified multi-walled carbon nanotube and carbon black mixture powder;
(2) adding the acidified multi-walled carbon nanotube and carbon black mixture powder obtained in the step (1) into ammonia water, and uniformly dispersing by ultrasonic to obtain a mixed solution I;
(3) adding ammonium metavanadate, ammonium metatungstate and cerous nitrate hexahydrate into a mixed solution of monoethanolamine and deionized water, and heating and dissolving to obtain a mixed solution II;
(4) adding the mixed solution I and the mixed solution II into a mixture containing titanium dioxide, silicon dioxide, glass fiber, stearic acid and pulp cotton under stirring, mixing, adding carboxymethyl cellulose, ethylene oxide and lactic acid, mixing again to obtain mixed pug, and aging;
(5) extruding, molding, drying and calcining the mixed pug obtained in the step (4) to obtain a target product;
and introducing mixed gas with the oxygen content of 30-50% in the calcining process, and keeping the whole calcining under the oxygen-enriched condition.
3. The method for preparing the honeycomb SCR denitration catalyst with the three-dimensional hierarchical pore structure according to claim 2, wherein the multi-walled carbon nanotubes in the step (1) have a diameter of 10-20 nm and a length of 5-15 μm; the particle size of the carbon black is 15-20 nm.
4. The method for preparing the honeycomb type SCR denitration catalyst with the three-dimensional hierarchical pore channel structure according to claim 2, wherein the mass ratio of the multi-wall carbon nano-tubes to the carbon black in the step (1) is 1: 1-5; the mass ratio of the total mass of the multi-wall carbon nano tubes and the carbon black to the mixed acid solution is 1: 5-10.
5. The method for preparing the honeycomb type SCR denitration catalyst with the three-dimensional multi-stage pore channel structure according to claim 4, wherein the mixed acid is formed by mixing concentrated sulfuric acid and concentrated nitric acid according to a volume ratio of 3: 1.
6. The method for preparing the honeycomb SCR denitration catalyst with the three-dimensional multi-stage pore channel structure according to claim 2, wherein the concentration of ammonia water in the step (2) is 15%, the ultrasonic dispersion power is 400-800W, and the time is 0.5-2 h.
7. The method for preparing the honeycomb type SCR denitration catalyst with the three-dimensional multi-stage pore channel structure according to claim 2, wherein the heating and dissolving temperature in the step (3) is 60-90 ℃.
8. The method for preparing the honeycomb SCR denitration catalyst with the three-dimensional multi-stage pore channel structure according to claim 2, wherein the mixture in the step (4) is stirred for 0.5-1 h before being added into the mixed solution I and the mixed solution II.
9. The method for preparing the honeycomb SCR denitration catalyst with the three-dimensional multi-stage pore channel structure according to claim 2, wherein the step (4) comprises the steps of adding the mixed solution (i) and the mixed solution (ii) into a mixture containing titanium dioxide, silicon dioxide, glass fiber, stearic acid and pulp cotton under stirring at a rotation speed of 200-400 rpm, mixing at a rotation speed of 600-800 rpm, uniformly mixing, adding carboxymethyl cellulose, ethylene oxide and lactic acid at 70-90 ℃, mixing at a rotation speed of 600-800 rpm again to obtain mixed pug, and aging for 12-48 hours.
10. The method for preparing the honeycomb type SCR denitration catalyst with the three-dimensional multi-stage pore channel structure according to claim 2, wherein the number of the honeycomb type catalyst pores extruded in the step (5) is 20 x 20 pores; the drying temperature is 20-60 ℃; and introducing mixed gas with the oxygen content of 30-50% in the calcining process, and keeping the whole calcining under the oxygen-enriched condition.
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| PCT/CN2019/126497 WO2020135202A1 (en) | 2018-12-27 | 2019-12-19 | Honeycomb scr denitration catalyst having three-dimensional hierarchical porous structure and preparation method |
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| CN109731569B (en) * | 2018-12-27 | 2021-12-10 | 安徽元琛环保科技股份有限公司 | Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof |
| CN111686716B (en) * | 2020-07-29 | 2022-06-14 | 江西省生态环境科学研究与规划院 | WOxLow-temperature SCR (selective catalytic reduction) flue gas denitration catalyst with modified carbon nano tube loaded with metal oxide, and preparation method and application thereof |
| CN112547045A (en) * | 2020-11-23 | 2021-03-26 | 安徽元琛环保科技股份有限公司 | Preparation method of photocatalytic denitration catalyst with porous titanium dioxide as carrier |
| CN114762835B (en) * | 2021-01-11 | 2023-07-28 | 中国石油化工股份有限公司 | Ozone catalytic oxidation catalyst for wastewater treatment and preparation method thereof |
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| CN113600168B (en) * | 2021-09-22 | 2023-08-11 | 大唐南京环保科技有限责任公司 | Low SO 2 Conversion rate honeycomb denitration catalyst and preparation method and application thereof |
| CN114011400B (en) * | 2021-10-21 | 2024-01-19 | 安徽元琛环保科技股份有限公司 | Preparation method of acidic system garbage incineration SCR denitration catalyst and denitration catalyst prepared by preparation method |
| CN114797837B (en) * | 2022-03-20 | 2023-03-10 | 浙江大学 | Catalyst capable of removing secondary pollutants in flue gas by concerted catalysis under low-temperature condition |
| CN116285128B (en) * | 2023-04-23 | 2024-01-12 | 罗孚橡胶（江苏）有限公司 | High-strength anti-aging rubber and preparation method thereof |
| CN116328789A (en) * | 2023-05-31 | 2023-06-27 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Chlorine poisoning resistant catalyst for simultaneously removing NO and VOCs and preparation method thereof |
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