CN114345381A - Preparation method of coating type denitration catalyst with modified honeycomb activated carbon as carrier and prepared catalyst - Google Patents
Preparation method of coating type denitration catalyst with modified honeycomb activated carbon as carrier and prepared catalyst Download PDFInfo
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- CN114345381A CN114345381A CN202111519570.8A CN202111519570A CN114345381A CN 114345381 A CN114345381 A CN 114345381A CN 202111519570 A CN202111519570 A CN 202111519570A CN 114345381 A CN114345381 A CN 114345381A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006255 coating slurry Substances 0.000 claims abstract description 28
- 239000011973 solid acid Substances 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 238000000498 ball milling Methods 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 23
- 239000004033 plastic Substances 0.000 claims description 21
- 229920003023 plastic Polymers 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 10
- 229920000609 methyl cellulose Polymers 0.000 claims description 8
- 239000001923 methylcellulose Substances 0.000 claims description 8
- 235000010981 methylcellulose Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 7
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 239000011230 binding agent Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 241000264877 Hippospongia communis Species 0.000 description 49
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
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- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
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- 239000012495 reaction gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical group [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Abstract
The invention discloses a preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier, which takes solid acid, activated carbon powder and a binder as raw materials and obtains modified activated carbon honeycomb ceramics through mixing, extrusion, drying and oxygen-free sintering; mixing and pulping vanadium pentoxide, titanium dioxide, molybdenum trioxide powder and acidic alumina sol, and adding nitric acid to adjust the pH value to obtain coating slurry; and uniformly coating the coating slurry on the surface of the modified activated carbon honeycomb ceramic by a dipping method. The invention also provides a catalyst prepared by the preparation method. According to the invention, the active carbon honeycomb carrier is subjected to solid acid modification to ensure that the active carbon honeycomb carrier has good surface acidity, and then the acidic coating slurry containing active substances is loaded on the active carbon honeycomb carrier, so that the solid acid modified honeycomb active carbon and the acidic coating slurry have excellent chemical bonding capability, the coating slurry and the active carbon carrier are combined more firmly, and the service life of the catalyst is prolonged.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier and a prepared catalyst.
Background
With the rapid development of modern industry, environmental problems are becoming more and more serious. Especially, the increase of the emission of nitrogen oxides (NOx) causes serious damage to the atmospheric environment and ecology of human beings. Therefore, the emission control of nitrogen oxides is one of the most urgent and necessary tasks in the field of atmospheric pollution control in China. Because the NOx control technology in China is developed late and not comprehensive enough, the problem of air pollution still becomes a focus and unsolved problem. Therefore, in recent years, the national standards increase the indexes of "denitration" in the requirements of pollutant emission control, strictly control the generation of NOx in industrial flue gas, and perform forced denitration. Therefore, the development and research of denitration techniques and methods thereof are not slow.
The flue gas denitration is a method for reducing the emission of nitrogen oxides which is generally adopted in the world at present, and can achieve high nitrogen oxide removal efficiency. Wherein, selective catalytic reduction method and selective non-catalytic reduction method are applied, and SCR technology can reach more than 90% of removal rate. There are also emerging methods, selective catalytic oxidation, low temperature plasma, etc. The Selective Catalytic Reduction (SCR) is the most widely used denitration method at home and abroad at the present time, and is first developed in the united states and then widely used in japan industry, and the method can make the removal efficiency of nitrogen oxides reach more than 90%. The basic principle of the SCR technology is that NOx in flue gas is reduced by reducing agents such as ammonia water and the like under the catalytic action of a catalyst to finally generate harmless N2。
At present, the mainstream denitration catalyst is a vanadium-tungsten-titanium system and is an extrusion-molded integral catalyst. Because the titanium dioxide is extracted from the ferrotitanium ore and is purified by the mainstream acid process, a large amount of energy is wasted in the process, acid pollution is caused, the acid treatment needs alkali neutralization, the obtained neutral salt wastewater causes secondary pollution, and the finding of the carrier replacing the titanium dioxide as the SCR denitration catalyst is an effective solution.
The activated carbon carrier can be made of biomass, and is a renewable environment-friendly material. If activated carbon is simply used as a support instead of titanium dioxide, the activity is greatly reduced. Therefore, the active substance coating using the activated carbon honeycomb as a carrier is a development object of many colleges, research institutions and manufacturers. Due to the inherent properties of substances such as titanium dioxide, tungsten trioxide, vanadium pentoxide and molybdenum trioxide, the coating slurry needs to be adjusted to be acidic, and thus active carbon is required to be used as a carrier and also needs to have certain acidity, so that the active substances can be stably coated on the surface of the carrier, and the active substances cannot fall off in the using process, so that the service life of the catalyst is not influenced.
At present, more activated carbon honeycombs are used as a coating type SCR denitration catalyst carrier. Patent CN1597094A is a catalyst prepared by adding phenolic resin or furan resin binder into activated carbon powder, extruding into a regular block with honeycomb structure, carbonizing, impregnating in ammonium metavanadate and oxalic acid mixed solution by an isometric impregnation method, drying, calcining, and oxidizing. Patent CN1792455A discloses a honeycomb activated carbon catalyst for flue gas denitrification, which is prepared by loading one or more metal oxides of iron, manganese and vanadium on the surface of honeycomb activated carbon by an isometric impregnation method. In patent CN102078753A, activated carbon is mixed with organic binder, forming aid and water, vacuum extrusion forming, drying and carbonization are performed to prepare honeycomb activated carbon carrier, manganese nitrate or mixed solution of manganese acetate and cerium nitrate is used as impregnation liquid, and the catalyst is prepared by adopting an isometric impregnation method. The activated carbon-based SCR denitration catalysts described in the above patents are all adjusted in formulation and are not optimized in acidic modification of the support.
Disclosure of Invention
The invention aims to solve the technical problem of how to solve the problem that the service life of the existing coating type denitration catalyst is influenced by falling off in the using process.
The invention solves the technical problems through the following technical means:
a preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier comprises the following steps:
(1) adding activated carbon powder, solid acid, methyl cellulose, polyethylene oxide and deionized water into a mixing roll according to the mass ratio of 100:1-5:3:2:30, uniformly mixing to obtain plastic pug, aging the obtained plastic pug overnight, adding the obtained plastic pug into an extruder provided with a filter screen and a honeycomb die, extruding and molding to obtain a wet blank, drying the wet blank to constant weight, and calcining under the protection of inert gas to obtain a solid acid modified honeycomb activated carbon carrier;
(2) mixing titanium dioxide, vanadium pentoxide and molybdenum trioxide according to a mass ratio of 79-89:5-10:6, carrying out wet ball milling on the obtained mixed powder in a ball mill by using an alumina sol solution as a solvent to obtain slurry with the average particle size of 10 mu m, and controlling the solid content of the slurry to be 30-50% by adjusting the adding amount of the alumina sol; taking out the slurry, adding nitric acid under the stirring condition, adjusting the pH to 1-4, and continuously stirring for 1h to obtain coating slurry;
(3) and (3) uniformly coating the coating slurry obtained in the step (2) on the surface of the modified activated carbon honeycomb ceramic prepared in the step (1) by adopting an impregnation method, controlling the loading amount to be 80-120g/L, drying the obtained sample to constant weight, heating to 300 ℃, and preserving heat for 4 hours to obtain the coating type denitration catalyst.
According to the invention, solid acid is added in the mixing stage of preparing the activated carbon honeycomb carrier, so that the activated carbon honeycomb carrier is subjected to solid acid modification in situ, the activated carbon honeycomb carrier has good surface acidity, and then the acidic coating slurry containing active substances is loaded on the activated carbon honeycomb carrier, so that the solid acid modified honeycomb activated carbon and the acidic coating slurry have excellent chemical bonding capacity, the coating slurry and the activated carbon carrier are combined more firmly, and the service life of the catalyst is prolonged.
Preferably, the specific surface area of the activated carbon powder in the step (1) is 800m2/g。
Preferably, the solid acid in step (1) comprises one of barium fluoride, strontium sulfate or phosphotungstic acid.
Preferably, the extrusion pressure in the step (1) is 3-5MPa, and the number of the die holes of the honeycomb die is 50-100 meshes.
Preferably, the drying temperature in the step (1) is 70-90 ℃, the calcining temperature is 500-700 ℃, and the calcining time is 5 h.
Preferably, the solid content of the alumina sol solution in the step (2) is 15%, and the solid particle size is 20-60 nm.
Preferably, the rotation speed of ball milling in the step (2) is 200-.
Preferably, the stirring in the step (2) is performed at normal temperature, and the stirring speed is 400-800 r/min.
Preferably, the temperature for drying in the step (3) is 50-70 ℃.
The invention also provides the denitration catalyst prepared by the preparation method.
The invention has the following beneficial effects:
1. according to the invention, solid acid is added in the mixing stage of preparing the activated carbon honeycomb carrier, so that the activated carbon honeycomb carrier is subjected to solid acid modification in situ, the activated carbon honeycomb carrier has good surface acidity, and then the acidic coating slurry containing active substances is loaded on the activated carbon honeycomb carrier, so that the solid acid modified honeycomb activated carbon and the acidic coating slurry have excellent chemical bonding capacity, the coating slurry and the activated carbon carrier are combined more firmly, and the service life of the catalyst is prolonged.
2. The coating slurry has adjustable components, and the honeycomb activated carbon-based coating type denitration catalyst with excellent ultralow-temperature denitration performance is obtained by adjusting the vanadium content in the active slurry; the activated carbon honeycomb is a renewable resource, and the carbon neutralization advantage is obvious.
Drawings
Fig. 1 is a graph showing the effect of solid acid modification of activated carbon honeycomb supports of examples of the present invention and comparative examples on the denitration stability of catalysts.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention will be described clearly and completely with reference to the accompanying drawings and embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Sources of test feed materials used in the following examples: aluminum sulfate and other raw materials are from China oil landification corporation, Lanzhou petrochemical company and are all industrial products; the template agent is purchased from Jinao chemical industry Co., Ltd, Anhui province, and is an industrial product, and the tetraethoxysilane and the methylcellulose are commercial reagents and are of industrial grade; other test materials and reagents, etc., are commercially available without specific reference.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier comprises the following steps:
(1) activated carbon powder (specific surface area 800 m) is mixed according to the mass ratio of 100:1:3:2:302Adding/g), barium fluoride, methyl cellulose, polyethylene oxide and deionized water into a mixing roll, uniformly mixing to obtain plastic pug, aging the obtained plastic pug overnight, adding the obtained plastic pug into an extruder provided with a filter screen and a honeycomb die, extruding and molding to obtain a wet blank, wherein the extrusion pressure is 3MPa, the number of holes of the die is 50 meshes, the wet blank is dried to constant weight at the temperature of 80 ℃, and is calcined under the protection of inert gas, the calcination temperature is 600 ℃, and the calcination time is 5 hours, so as to obtain a solid acid modified honeycomb activated carbon carrier;
(2) mixing titanium dioxide, vanadium pentoxide and molybdenum trioxide according to a mass ratio of 89:5:6, carrying out wet ball milling on the obtained mixed powder in a ball mill by taking an alumina sol solution (the solid content in the alumina sol solution is 15%, and the solid particle size is 20-60nm) as a solvent, wherein the ball milling rotation speed is 200r/min, the ball milling time is 2h, the ball milling temperature is 30 ℃, obtaining slurry with the average particle size of 10 mu m, and controlling the solid content of the slurry to be 30% by adjusting the adding amount of the alumina sol; taking out the slurry, adding nitric acid under stirring (stirring at normal temperature and stirring speed of 400r/min), adjusting the pH to 1-2, and continuously stirring for 1h to obtain coating slurry;
(3) and (3) uniformly coating the coating slurry obtained in the step (2) on the surface of the modified activated carbon honeycomb ceramic prepared in the step (1) by adopting an impregnation method, controlling the loading amount to be 80g/L, drying the obtained sample at 60 ℃ to constant weight, heating to 300 ℃, and preserving heat for 4 hours to obtain the coating type denitration catalyst.
Example 2
A preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier comprises the following steps:
(1) activated carbon powder (specific surface area 800 m) is mixed according to the mass ratio of 100:3:3:2:302Adding/g), barium fluoride, methyl cellulose, polyethylene oxide and deionized water into a mixing roll, uniformly mixing to obtain plastic pug, aging the obtained plastic pug overnight, adding the obtained plastic pug into an extruder provided with a filter screen and a honeycomb die, extruding and molding to obtain a wet blank, wherein the extrusion pressure is 3MPa, the number of holes of the die is 50 meshes, the wet blank is dried to constant weight at the temperature of 80 ℃, and is calcined under the protection of inert gas, the calcination temperature is 600 ℃, and the calcination time is 5 hours, so as to obtain a solid acid modified honeycomb activated carbon carrier;
(2) mixing titanium dioxide, vanadium pentoxide and molybdenum trioxide according to a mass ratio of 84:10:6, carrying out wet ball milling on the obtained mixed powder in a ball mill by taking an alumina sol solution (the solid content in the alumina sol solution is 15%, and the solid particle size is 20-60nm) as a solvent, wherein the ball milling rotation speed is 200r/min, the ball milling time is 2h, the ball milling temperature is 30 ℃, obtaining slurry with the average particle size of 10 mu m, and controlling the solid content of the slurry to be 40% by adjusting the adding amount of the alumina sol; taking out the slurry, adding nitric acid under stirring (stirring at normal temperature and stirring speed of 400r/min), adjusting the pH to 2-3, and continuously stirring for 1h to obtain coating slurry;
(3) and (3) uniformly coating the coating slurry obtained in the step (2) on the surface of the modified activated carbon honeycomb ceramic prepared in the step (1) by adopting an impregnation method, controlling the loading amount to be 100g/L, drying the obtained sample at 60 ℃ to constant weight, heating to 300 ℃, and preserving heat for 4 hours to obtain the coating type denitration catalyst.
Example 3
A preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier comprises the following steps:
(1) activated carbon powder (specific surface area 800 m) is mixed according to the mass ratio of 100:5:3:2:302Adding/g), barium fluoride, methyl cellulose, polyethylene oxide and deionized water into a mixing roll, uniformly mixing to obtain plastic pug, aging the obtained plastic pug overnight, adding the obtained plastic pug into an extruder provided with a filter screen and a honeycomb die, extruding and molding to obtain a wet blank, wherein the extrusion pressure is 3MPa, the number of holes of the die is 50 meshes, the wet blank is dried to constant weight at the temperature of 80 ℃, and is calcined under the protection of inert gas, the calcination temperature is 600 ℃, and the calcination time is 5 hours, so as to obtain a solid acid modified honeycomb activated carbon carrier;
(2) mixing titanium dioxide, vanadium pentoxide and molybdenum trioxide according to a mass ratio of 79:15:6, carrying out wet ball milling on the obtained mixed powder in a ball mill by taking an alumina sol solution (the solid content in the alumina sol solution is 15%, and the solid particle size is 20-60nm) as a solvent, wherein the ball milling rotation speed is 200r/min, the ball milling time is 2h, the ball milling temperature is 30 ℃, obtaining slurry with the average particle size of 10 mu m, and controlling the solid content of the slurry to be 50% by adjusting the adding amount of the alumina sol; taking out the slurry, adding nitric acid under stirring conditions (stirring at normal temperature and the stirring speed of 400r/min), adjusting the pH value to 3-4, and continuously stirring for 1h to obtain coating slurry;
(3) and (3) uniformly coating the coating slurry obtained in the step (2) on the surface of the modified activated carbon honeycomb ceramic prepared in the step (1) by adopting an impregnation method, controlling the loading amount to be 120g/L, drying the obtained sample at 60 ℃ to constant weight, heating to 300 ℃, and preserving heat for 4 hours to obtain the coating type denitration catalyst.
Example 4
A preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier comprises the following steps:
(1) activated carbon powder (specific surface area 800 m) is mixed according to the mass ratio of 100:5:3:2:302Per gram), barium fluoride,Adding methyl cellulose, polyethylene oxide and deionized water into a mixing roll, uniformly mixing to obtain plastic pug, aging the obtained plastic pug overnight, adding the obtained plastic pug into an extruder provided with a filter screen and a honeycomb die, extruding and molding to obtain a wet blank, wherein the extrusion pressure is 3MPa, the number of die holes is 50 meshes, the wet blank is dried to constant weight at 80 ℃, and is calcined under the protection of inert gas, the calcination temperature is 600 ℃, and the calcination time is 5 hours, so as to obtain a solid acid modified honeycomb activated carbon carrier;
(2) mixing titanium dioxide, vanadium pentoxide and molybdenum trioxide according to a mass ratio of 79:15:6, carrying out wet ball milling on the obtained mixed powder in a ball mill by taking an alumina sol solution (the solid content in the alumina sol solution is 15%, and the solid particle size is 20-60nm) as a solvent, wherein the ball milling rotation speed is 200r/min, the ball milling time is 2h, the ball milling temperature is 30 ℃, obtaining slurry with the average particle size of 10 mu m, and controlling the solid content of the slurry to be 50% by adjusting the adding amount of the alumina sol; taking out the slurry, adding nitric acid under stirring (stirring at normal temperature and stirring speed of 400r/min), adjusting the pH to 1-2, and continuously stirring for 1h to obtain coating slurry;
(3) and (3) uniformly coating the coating slurry obtained in the step (2) on the surface of the modified activated carbon honeycomb ceramic prepared in the step (1) by adopting an impregnation method, controlling the loading amount to be 120g/L, drying the obtained sample at 60 ℃ to constant weight, heating to 300 ℃, and preserving heat for 4 hours to obtain the coating type denitration catalyst.
Example 5
A preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier comprises the following steps:
(1) activated carbon powder (specific surface area 800 m) is mixed according to the mass ratio of 100:5:3:2:302Adding/g), barium fluoride, methyl cellulose, polyethylene oxide and deionized water into a mixing roll to be uniformly mixed to obtain plastic pug, aging the obtained plastic pug overnight, adding the obtained plastic pug into an extruder provided with a filter screen and a honeycomb die to be extruded and molded to obtain a wet blank, wherein the extrusion pressure is 3MPa, the number of holes of the die is 50 meshes, the wet blank is dried to constant weight at the temperature of 80 ℃, and is calcined under the protection of inert gas, the calcination temperature is 600 ℃, the calcination time is 5 hours, and a solid is obtainedAn acid-modified honeycomb activated carbon support;
(2) mixing titanium dioxide, vanadium pentoxide and molybdenum trioxide according to a mass ratio of 79:15:6, carrying out wet ball milling on the obtained mixed powder in a ball mill by taking an alumina sol solution (the solid content in the alumina sol solution is 15%, and the solid particle size is 20-60nm) as a solvent, wherein the ball milling rotation speed is 200r/min, the ball milling time is 2h, the ball milling temperature is 30 ℃, obtaining slurry with the average particle size of 10 mu m, and controlling the solid content of the slurry to be 30% by adjusting the adding amount of the alumina sol; taking out the slurry, adding nitric acid under stirring conditions (stirring at normal temperature and the stirring speed of 400r/min), adjusting the pH value to 3-4, and continuously stirring for 1h to obtain coating slurry;
(3) and (3) uniformly coating the coating slurry obtained in the step (2) on the surface of the modified activated carbon honeycomb ceramic prepared in the step (1) by adopting an impregnation method, controlling the loading amount to be 80g/L, drying the obtained sample at 60 ℃ to constant weight, heating to 300 ℃, and preserving heat for 4 hours to obtain the coating type denitration catalyst.
Comparative example
This comparative example differs from example 3 in that: solid acid is not added in the raw materials when the honeycomb activated carbon carrier is prepared.
The other steps and process parameters were the same as in example 3.
In the above examples, the kind and amount of solid acid added to the activated carbon honeycomb carrier were examined, the vanadium content, pH and solid content in the coating slurry were adjusted, and the amount of active material loaded on the coated carrier was examined.
The denitration catalysts prepared in the above examples and comparative examples were subjected to denitration performance test: carrying out denitration performance test in a fixed bed, cutting a catalyst into samples with the sizes of 20mm multiplied by 30mm along the pore channel direction, and putting the samples into a bed layer along the axis of a reactor; the components of the flue gas are NO (1000ppm) and NH3(1000ppm)、O2(6vol.％)、N2As carrier gas, the airspeed of the mixed gas is 6000h-1(ii) a The reaction temperature is 150 ℃, before the reaction gas is introduced, air is introduced into the fixed bed reactor, the temperature is raised to 400 ℃ and kept for 4 hours, the temperature is reduced to 150 ℃, and then the reaction gas is introduced for removingThe nitrate property test results are shown in FIG. 1.
According to the results of fig. 1, it can be seen that the denitration catalyst with the solid acid modified activated carbon honeycomb as a carrier for coating the active substance has no obvious inactivation in the reaction time of nearly 100 hours, and has obvious service life advantage; the catalyst of the comparative group which had not been subjected to the solid acid modification rapidly deactivated with the lapse of time although the initial activity was the same as that of the solid acid-modified sample in the example; fully shows that the solid acid modification of the activated carbon can improve the bonding firmness between the coating layer and the carrier and prevent the active substances from being blown and dropped by high-speed airflow in the reaction, thereby improving the physical strength of the catalyst and prolonging the service life; in addition, the catalyst in example 3 has a nitrogen oxide removal rate of 95% or more at 150 ℃, and has excellent ultra-low temperature catalytic denitration performance.
The influence of solid content, load capacity and pH on the denitration activity of the catalyst is simultaneously considered, the result is shown in Table 1, the influence of the denitration activity of the catalyst and the change of the pH is not large as can be seen from Table 1, and the pH can meet the activity requirement within the range of 1-4; the denitration activity of the catalyst is in direct proportion to the content, solid content and loading capacity of vanadium in the slurry.
Table 1 shows the influence of the solid content, the loading amount and the pH on the denitration activity of the catalyst in the examples of the present invention
| Example 3 | Example 4 | Example 5 | |
| Initial Denitrification Activity (%) | 94.1 | 93.9 | 81.2 |
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a coating type denitration catalyst taking modified honeycomb activated carbon as a carrier is characterized by comprising the following steps:
(1) adding activated carbon powder, solid acid, methyl cellulose, polyethylene oxide and deionized water into a mixing roll according to the mass ratio of 100:1-5:3:2:30, uniformly mixing to obtain plastic pug, aging the obtained plastic pug overnight, adding the obtained plastic pug into an extruder provided with a filter screen and a honeycomb die, extruding and molding to obtain a wet blank, drying the wet blank to constant weight, and calcining under the protection of inert gas to obtain a solid acid modified honeycomb activated carbon carrier;
(2) mixing titanium dioxide, vanadium pentoxide and molybdenum trioxide according to a mass ratio of 79-89:5-10:6, carrying out wet ball milling on the obtained mixed powder in a ball mill by using an alumina sol solution as a solvent to obtain slurry with the average particle size of 10 mu m, and controlling the solid content of the slurry to be 30-50% by adjusting the adding amount of the alumina sol; taking out the slurry, adding nitric acid under the stirring condition, adjusting the pH to 1-4, and continuously stirring for 1h to obtain coating slurry;
(3) and (3) uniformly coating the coating slurry obtained in the step (2) on the surface of the modified activated carbon honeycomb ceramic prepared in the step (1) by adopting an impregnation method, controlling the loading amount to be 80-120g/L, drying the obtained sample to constant weight, heating to 300 ℃, and preserving heat for 4 hours to obtain the coating type denitration catalyst.
2. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: the specific surface area of the activated carbon powder in the step (1) is 800m2/g。
3. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: the solid acid in the step (1) comprises one of barium fluoride, strontium sulfate or phosphotungstic acid.
4. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: in the step (1), the extrusion pressure is 3-5MPa, and the number of the die holes of the honeycomb die is 50-100 meshes.
5. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: the drying temperature in the step (1) is 70-90 ℃, the calcining temperature is 500-700 ℃, and the calcining time is 5 h.
6. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: in the step (2), the solid content of the alumina sol solution is 15%, and the solid particle size is 20-60 nm.
7. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: the rotation speed of ball milling in the step (2) is 200-.
8. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: stirring is carried out in the step (2) at normal temperature, and the stirring rotating speed is 400-800 r/min.
9. The preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to claim 1, is characterized in that: the drying temperature in the step (3) is 50-70 ℃.
10. The denitration catalyst prepared by the preparation method of the coating-type denitration catalyst taking the modified honeycomb activated carbon as the carrier according to any one of claims 1 to 9.
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