CN110639502A - SCR denitration catalyst with high thermal shock resistance for honeycomb ship and preparation method thereof - Google Patents
SCR denitration catalyst with high thermal shock resistance for honeycomb ship and preparation method thereof Download PDFInfo
- Publication number
- CN110639502A CN110639502A CN201910917688.2A CN201910917688A CN110639502A CN 110639502 A CN110639502 A CN 110639502A CN 201910917688 A CN201910917688 A CN 201910917688A CN 110639502 A CN110639502 A CN 110639502A
- Authority
- CN
- China
- Prior art keywords
- thermal shock
- catalyst
- shock resistance
- scr denitration
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 230000035939 shock Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 229910000174 eucryptite Inorganic materials 0.000 claims abstract description 10
- 229910052642 spodumene Inorganic materials 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000006184 cosolvent Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000012744 reinforcing agent Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- -1 polyoxyethylene, methyl Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
Abstract
The invention discloses an SCR denitration catalyst for a high thermal shock resistance honeycomb ship and a preparation method thereof, wherein the catalyst comprises the following components in parts by weight: 40-80 parts of carrier nano titanium dioxide, gamma-Al2O35-10 parts of active component, 5-30 parts of active additive, 2-10 parts of structural additive and deionized water. The SCR denitration catalyst for the honeycomb ship with high thermal shock resistance is prepared by taking anatase type nano titanium dioxide and active gamma-alumina spheres as carriers, ammonium metavanadate and cerium nitrate as active precursors, taking glass fiber, spodumene, eucryptite and the like with specific specifications as structural reinforcing agents, adding forming aids such as an adhesive, a lubricant and the like, mixing, extruding into a blank, drying and calcining. The inventionThe thermal shock resistance of the marine SCR denitration catalyst is improved, the appearance of the catalyst is kept intact after 30 times of rapid heating-cooling thermal shock circulation at 25-550 ℃, and the denitration efficiency is still kept above 80%.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an SCR denitration catalyst for a high-thermal shock resistance honeycomb ship and a preparation method thereof.
Background
With the continuous enhancement of environmental protection consciousness of the whole society, the international requirement on the ship tail gas emission is stricter and stricter. The International Maritime Organization (IMO) maritime environmental protection committee at 66's meeting (MEPC66) stipulates that since 2016, 1/1, a newly manufactured ship must meet Tier III standards for diesel engines installed on newly manufactured ships, requiring that the amount of NOx emissions from the ship's tail gas be reduced by 80% compared to Tier I, and that the exhaust gas generated by ships traveling in emission control areas must meet this new standard.
The Selective Catalytic Reduction (SCR) technology becomes an effective way to realize Tier III standard by virtue of the advantages of high NOx conversion efficiency, good fuel economy, wide application range, and the like. The core of an SCR system is the SCR catalyst, and the operating costs of an SCR plant are largely dependent on the life of the catalyst.
Because the tail gas temperature of the marine diesel engine is large in temperature fluctuation when the marine diesel engine is frequently started and stopped and idled and is under low load and high load, the upper limit of the exhaust temperature of the marine diesel engine can reach 500 ℃ in a full load state, and the lower limit of the exhaust temperature of the marine diesel engine can be lower than 200 ℃ in the low load and idle state. In an environment with frequent and large temperature variation, the use problems of the SCR catalyst mainly include: influenced by sudden heating and quenching, cracks are easily generated on the surface, so that the structural strength of the catalyst is reduced, the service life of a catalyst module is influenced, and the operation cost of ship denitration is increased. Furthermore, frequent temperature changes also reduce the activity of the catalyst.
Disclosure of Invention
The invention aims to provide a high-thermal-shock-resistance SCR denitration catalyst for a honeycomb ship and a preparation method thereof, and aims to solve the technical problems of poor thermal shock resistance, low denitration stability, short service life of a catalyst module and high operation cost of ship denitration of the conventional commercial denitration catalyst for the ship.
In order to achieve the purpose, the invention adopts the following technical scheme: the invention provides an SCR denitration catalyst for a high-thermal shock resistance honeycomb ship, which comprises the following components in parts by weight: 40-80 parts of carrier nano titanium dioxide, gamma-Al2O35-10 parts of active component, 5-30 parts of active additive, 2-10 parts of structural additive and deionized water.
Further comprises a forming assistant and a pore-forming agent.
Further, the forming auxiliary agent is an adhesive and a lubricant; 5-20 parts of a forming aid.
Further, the active component is one or more of vanadium, tungsten, molybdenum and cerium.
Further, the active additive is one or more of ammonium molybdate, molybdenum oxide, ammonium tungstate and tungsten oxide.
Further, the structural auxiliary agent is one or more of glass fiber, spodumene and eucryptite. The spodumene has low thermal expansion, and the calcined spodumene can improve the structural lattice in the catalyst, can offset partial internal stress of the material when the material is subjected to thermal shock, and improves the thermal shock resistance of the material. Beta-eucryptite is one of the few substances in nature with negative coefficients of expansion, which, in contrast to most materials, decreases in volume with increasing temperature. Due to the additive property of the thermal expansion coefficient of the material, the beta-eucryptite enables the whole material to show the performance of low expansion or zero expansion, thereby improving the thermal stability and thermal shock resistance of the material.
The invention also provides a preparation method of the SCR denitration catalyst for the honeycomb ship with high thermal shock resistance, which comprises the following specific steps:
step one, preparing an active precursor solution;
secondly, adding carrier titanium dioxide, alumina, active auxiliary agent, structural auxiliary agent A, ammonia water and deionized water into a stirrer for high-speed stirring and mulling; the mass ratio of the carrier titanium dioxide, the alumina, the active assistant, the structural assistant A, the ammonia water and the deionized water is 40-80: 5-10: 2-10: 0-10: 5-20: 50-150;
step three, sequentially adding a lubricant, a structural assistant B, a pore-forming agent and an active precursor solution into the pug obtained in the step two, sealing, stirring at a high speed, heating to 80 ℃, preserving heat for 1-2h, cooling, then adding 0-10 adhesive, stirring for 20-30min, uniformly mixing, and adjusting the water content of the final pug to be 20-38% and the pH to be 7.0-9.8 by adding ammonia water and deionized water;
wherein the mass ratio of the lubricant to the structural assistant B to the pore-forming agent to the active precursor solution is 0-5: 5-15: 1-10: 10-50 parts of;
step four, after the pug obtained in the step three is aged for 10-48 hours in a sealed environment, filtering out impurities in the pug by adopting a filter screen with the specification of 1mm multiplied by 15mm, and preliminarily extruding into pug blocks; sealing and ageing the slurry in a material box for 8-24h, and extruding the slurry block material into a catalyst blank by extrusion equipment;
step five, gradually heating, dehumidifying and drying the extruded catalyst blank under the environment with the humidity of 40-80%, wherein the heating rate is 2-10 ℃/h, the initial temperature is 20 ℃ at room temperature, and the humidity is 80%; keeping the temperature and moisture at 60-80 deg.C and 40% humidity for 20-48 h;
and step six, calcining in a muffle furnace to obtain the high thermal shock resistance marine SCR denitration catalyst.
Further, in the step one, preparation of an active precursor solution: dissolving ammonium metavanadate and cerium nitrate into deionized water, and adding an alkaline cosolvent to completely dissolve the ammonium metavanadate and the cerium nitrate to obtain the cerium nitrate;
wherein the mass ratio of ammonium metavanadate to cerium nitrate is 5-25: 1-10; the addition amount of the alkaline cosolvent is 0 to 10 weight parts.
Further, after the SCR catalyst is subjected to thermal shock circulation for 30 times at 550 ℃, the denitration activity is over 80 percent.
Further, the calcination process in the step six:
firstly, placing a dried sample in a muffle furnace, gradually heating the sample from room temperature to 200 ℃, wherein the heating rate is 1-10 ℃/min;
secondly, keeping the temperature at 200 ℃ for 3-6 h;
thirdly, gradually heating from 200 ℃ to 620 ℃, wherein the heating rate is 50-100 ℃/h, and then preserving heat for 3-12 h; fourthly, after the calcination is completed, the mixture is gradually cooled to the room temperature.
Further, the carrier titanium dioxide is anatase titanium dioxide.
Further, the alumina is active gamma-Al2O3And (3) microspheres.
Further, the adhesive is one or more of polyethylene oxide, methyl cellulose ammonium and sesbania powder.
Further, the alkaline cosolvent is ethanolamine or triethanolamine.
Further, the pore-forming agent is one or more of cotton pulp, sesbania powder and carbon powder. Volatile carbon dioxide is generated when the pore-forming agent which is uniformly dispersed in the catalyst blank is calcined, rich macropores and mesopores are formed, and the specific surface area of the catalyst is effectively increased.
Further, the lubricant is one or more of stearic acid, glycerol, tung oil and palm oil. By adopting the proper lubricant, the fluidity of the pug can be increased, the extrusion pressure of the pug can be reduced, and the smooth extrusion of the surface of the extruded blank body can be ensured.
Further, the glass fiber is a structural reinforcing material; the length of the utility model is 3-8mm, and the diameter is 0-30 μm. The glass fiber with short length is adopted, so that the glass fiber can smoothly pass through a compact filter screen without being intercepted on the filter screen during filtering and extrusion, and is more uniformly dispersed in pug, and the mechanical strength of the catalyst is improved.
The invention has the beneficial effects that:
the SCR denitration catalyst for the honeycomb ship with high thermal shock resistance and the preparation method thereof have better thermal shock resistance, and the catalyst has longer physical life and higher mechanical strength under the same thermal shock environment.
2, the high thermal shock resistance honeycomb ship SCR denitration catalyst and the preparation method thereof provided by the invention have higher and more stable denitration activity than a conventional catalyst in a simulated thermal shock environment after a certain time, thereby greatly prolonging the service life of the ship SCR and reducing the cost of ship denitration. Better denitration stability and high denitration activity.
3, the catalyst can maintain better working performance in an environment with frequent temperature change, and the service life of the catalyst module is prolonged.
4, the catalyst provided by the invention takes nano titanium dioxide and gamma-alumina as active carriers, takes short glass fiber as a structure reinforcing material, spodumene and eucryptite as stabilizers, and takes vanadium, cerium, tungsten and molybdenum metal elements as main active components. The denitration activity of the prepared SCR catalyst is still over 80 percent after 30 times of thermal shock at 550 ℃.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The primary objects and other advantages of the invention may be realized and attained by the instrumentalities particularly pointed out in the specification.
Detailed Description
The technical solutions of the present invention are described in detail below by examples, and the following examples are only exemplary and can be used only for explaining and explaining the technical solutions of the present invention, but not construed as limiting the technical solutions of the present invention.
The invention provides a preparation method of a marine SCR denitration catalyst with high thermal shock resistance on the basis of an original SCR catalyst, aiming at the problem of poor thermal shock resistance of the existing commercial marine denitration catalyst.
Specifically, the weight parts of the catalyst are as follows: 40 to 80 portions of carrier nanometer titanium dioxide,
γ-Al2O3the weight ratio of the components is 5-10 parts,
5-30 parts of active component, wherein the active component can be one or more of vanadium, tungsten, molybdenum and cerium;
2-10 parts of active additive, wherein the active additive can be one or more of ammonium molybdate, molybdenum oxide, ammonium tungstate and tungsten oxide;
5-40 parts of a structural auxiliary agent, wherein the structural auxiliary agent can be one or more of glass fiber, spodumene and eucryptite. The spodumene has low thermal expansion, and the calcined spodumene can improve the structural lattice in the catalyst, can offset partial internal stress of the material when the material is subjected to thermal shock, and improves the thermal shock resistance of the material. Beta-eucryptite is one of the few substances in nature with negative coefficients of expansion, which, in contrast to most materials, decreases in volume with increasing temperature. Due to the additive property of the thermal expansion coefficient of the material, the beta-eucryptite enables the whole material to show the performance of low expansion or zero expansion, thereby improving the thermal stability and thermal shock resistance of the material.
The glass fibers may be structural reinforcing materials; the length of the utility model is 3-8mm, and the diameter is 0-30 μm. The glass fiber with short length is adopted, so that the glass fiber can smoothly pass through a compact filter screen without being intercepted on the filter screen during filtering and extrusion, and is more uniformly dispersed in pug, and the mechanical strength of the catalyst is improved.
5-20 parts of forming auxiliary agents, wherein the forming auxiliary agents can be adhesives and lubricants; and deionized water and pore-forming agent. The adhesive is one or more of polyoxyethylene, methyl cellulose ammonium and sesbania powder. The pore-forming agent can be one or more of cotton pulp, sesbania powder and carbon powder. Volatile carbon dioxide is generated when the pore-forming agent which is uniformly dispersed in the catalyst blank is calcined, rich macropores and mesopores are formed, and the specific surface area of the catalyst is effectively increased.
The lubricant can be one or more of stearic acid, glycerol, tung oil and palm oil. By adopting the proper lubricant, the fluidity of the pug can be increased, the extrusion pressure of the pug can be reduced, and the smooth extrusion of the surface of the extruded blank body can be ensured.
The preparation method of the SCR denitration catalyst for the honeycomb ship with high thermal shock resistance comprises the following specific steps:
step one, preparing an active precursor solution; preparing an active precursor solution: dissolving ammonium metavanadate and cerium nitrate into deionized water, and adding an alkaline cosolvent to completely dissolve the ammonium metavanadate and the cerium nitrate to obtain the cerium nitrate;
wherein the mass ratio of ammonium metavanadate to cerium nitrate is 5-25: 1-10; the addition amount of the alkaline cosolvent is 0 to 10 weight parts. The basic cosolvent can be ethanolamine or triethanolamine.
Secondly, adding carrier titanium dioxide, alumina, active auxiliary agent, structural auxiliary agent A, ammonia water and deionized water into a stirrer for high-speed stirring and mulling; the mass ratio of the carrier titanium dioxide, the alumina, the active assistant, the structural assistant A, the ammonia water and the deionized water is 40-80: 5-10: 2-10: 0-10: 5-20: 50-150; the carrier titanium dioxide can be anatase titanium dioxide. The alumina can be active gamma-Al2O3And (3) microspheres.
Step three, sequentially adding a lubricant, a structural assistant B, a pore-forming agent and an active precursor solution into the pug obtained in the step two, sealing, stirring at a high speed, heating to 80 ℃, preserving heat for 1-2h, cooling, then adding 0-10 adhesive, stirring for 20-30min, uniformly mixing, and adjusting the water content of the final pug to be 20-38% and the pH to be 7.0-9.8 by adding ammonia water and deionized water;
wherein the mass ratio of the lubricant to the structural assistant B to the pore-forming agent to the active precursor solution is 0-5: 5-15: 1-10: 10-50 parts of;
step four, after the pug obtained in the step three is aged for 10-48 hours in a sealed environment, filtering out impurities in the pug by adopting a filter screen with the specification of 1mm multiplied by 15mm, and preliminarily extruding into pug blocks; sealing and ageing the slurry in a material box for 8-24h, and extruding the slurry block material into a catalyst blank by extrusion equipment;
step five, gradually heating, dehumidifying and drying the extruded catalyst blank under the environment with the humidity of 40-80%, wherein the heating rate is 2-10 ℃/h, the initial temperature is 20 ℃ at room temperature, and the humidity is 80%; keeping the temperature and moisture at 60-80 deg.C and 40% humidity for 20-48 h;
and step six, calcining in a muffle furnace to obtain the high thermal shock resistance marine SCR denitration catalyst. After the SCR catalyst is subjected to thermal shock circulation for 30 times at 550 ℃, the denitration activity is over 80 percent.
And the calcination process in the step six: firstly, placing a dried sample in a muffle furnace, gradually heating the sample from room temperature to 200 ℃, wherein the heating rate is 1-10 ℃/min; secondly, keeping the temperature at 200 ℃ for 3-6 h; thirdly, gradually heating from 200 ℃ to 620 ℃, wherein the heating rate is 50-100 ℃/h, and then preserving heat for 3-12 h; fourthly, after the calcination is completed, the mixture is gradually cooled to the room temperature.
Table 1 details of the components of examples 1-3 and the control
The above examples 1-3 were characterized:
1, thermal shock resistance evaluation: the catalyst sample prepared in the embodiment of the invention is subjected to thermal shock resistance evaluation. According to the working environment commonly used by the marine SCR denitration catalyst, the thermal shock temperature range of the test is selected to be 25-550 ℃. Putting the sample into a muffle furnace at 550 ℃ from room temperature, preserving the heat for 20min to uniformly heat the surface and the interior of the sample, then taking out the sample, rapidly cooling the sample in flowing water at 20 ℃, and observing whether the sample cracks or not to detect the thermal shock resistance of the sample. If the sample did not crack, the heating-cooling was repeated until the sample cracked, and the number of repetitions was recorded, and the results are shown in table 2 below.
TABLE 2 thermal shock resistance test
| Item | Number of thermal shock cycles at crack occurrence |
| Example 1 | 30 |
| Example 2 | 38 |
| Example 3 | 36 |
| Control sample | 20 |
2, evaluation of catalyst performance: the catalyst obtained in the example was cut into 30mm × 30mm × 300mm samples, and then subjected to the same number of heating-cooling cycle thermal shock tests (cycle number is based on the number of earliest cracks in one of the samples). And then, respectively carrying out a simulated flue gas denitration test on each sample subjected to the thermal shock test. And (3) testing conditions are as follows: simulated flue gas flow rate of 33800h-1The NOx concentration at the inlet of flue gas is 280 deg.C, 300 deg.C and 350 deg.C.
TABLE 3 Denitrification Activity of the samples
As can be seen from the above table 3, the thermal shock resistance of the marine SCR denitration catalyst prepared by the method is remarkably improved, and the thermal shock cycle number is improved by 50-80%. After thermal shock circulation, the catalyst prepared by the method has stable denitration efficiency, and compared with a blank sample, the denitration efficiency is higher.
The catalyst has larger catalytic reaction surface area in unit volume, and directly improves the catalytic efficiency. On the surface of the conventional SCR denitration catalyst, active components are in a stacking state, so that the waste of the active components is caused, the gas adsorption process in a microporous structure of the catalyst is influenced, and the catalytic reaction efficiency is reduced. Therefore, the active components in the thin-wall catalyst can be more uniformly distributed on the surface of the catalyst, and the catalytic efficiency is indirectly improved.
According to the invention, anatase type nano titanium dioxide and active gamma-alumina spheres are used as carriers, ammonium metavanadate and cerium nitrate are used as active precursors, glass fiber, spodumene, eucryptite and the like with specific specifications are used as structural reinforcing agents, molding aids such as adhesives and lubricants are added, the materials are mixed and extruded into blanks, and the blanks are dried and calcined to obtain the high thermal shock resistance SCR denitration catalyst for the honeycomb ship. The invention improves the thermal shock resistance of the marine SCR denitration catalyst, and after 30 times of rapid heating-cooling thermal shock circulation at 25-550 ℃, the appearance of the catalyst is kept intact, and the denitration efficiency is still kept above 80%. The SCR denitration catalyst for the high-thermal shock resistance honeycomb ship, which is prepared by the invention, has good thermal shock resistance, overcomes the problem of damage to the physical structure of the catalyst caused by frequent start and stop of the ship, and prolongs the service life of the catalyst.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that may be made by those skilled in the art within the technical scope of the present invention will be covered by the scope of the present invention.
Claims (10)
1. High thermal shock resistance honeycomb marine SCR denitration catalyst which characterized in that: the catalyst comprises the following components in parts by weight: 40-80 parts of carrier nano titanium dioxide, gamma-Al2O35-10 parts of active component, 5-30 parts of active additive, 2-10 parts of structural additive and deionized water.
2. The SCR denitration catalyst for the high-thermal shock resistance honeycomb ship as recited in claim 1, further comprising a forming aid and a pore-forming agent.
3. The SCR denitration catalyst for the honeycomb ship with the high thermal shock resistance as recited in claim 2, wherein the molding aids are an adhesive and a lubricant; 5-20 parts of a forming aid.
4. The SCR denitration catalyst for the high-thermal shock resistance honeycomb ship as recited in claim 1, wherein the active component is one or more of vanadium, tungsten, molybdenum and cerium.
5. The SCR denitration catalyst for the high-thermal shock resistance honeycomb ship as recited in claim 1, wherein the active assistant is one or more of ammonium molybdate, molybdenum oxide, ammonium tungstate and tungsten oxide.
6. The SCR denitration catalyst for the high-thermal shock resistance honeycomb ship as recited in claim 1, wherein the structural auxiliary agent is one or more of glass fiber, spodumene and eucryptite.
7. The preparation method of the SCR denitration catalyst for the honeycomb ship with the high thermal shock resistance as recited in any one of claims 1 to 6, characterized by comprising the following steps:
step one, preparing an active precursor solution;
secondly, adding carrier titanium dioxide, alumina, active auxiliary agent, structural auxiliary agent A, ammonia water and deionized water into a stirrer for high-speed stirring and mulling; the mass ratio of the carrier titanium dioxide, the alumina, the active assistant, the structural assistant A, the ammonia water and the deionized water is 40-80: 5-10: 2-10: 0-10: 5-20: 50-150;
step three, sequentially adding a lubricant, a structural assistant B, a pore-forming agent and an active precursor solution into the pug obtained in the step two, sealing, stirring at a high speed, heating to 80 ℃, preserving heat for 1-2h, cooling, then adding 0-10 adhesive, stirring for 20-30min, uniformly mixing, and adjusting the water content of the final pug to be 20-38% and the pH to be 7.0-9.8 by adding ammonia water and deionized water;
wherein the mass ratio of the lubricant to the structural assistant B to the pore-forming agent to the active precursor solution is 0-5: 5-15: 1-10: 10-50 parts of;
step four, after the pug obtained in the step three is aged for 10-48 hours in a sealed environment, filtering out impurities in the pug by adopting a filter screen with the specification of 1mm multiplied by 15mm, and preliminarily extruding into pug blocks; sealing and ageing the slurry in a material box for 8-24h, and extruding the slurry block material into a catalyst blank by extrusion equipment;
step five, gradually heating, dehumidifying and drying the extruded catalyst blank under the environment with the humidity of 40-80%, wherein the heating rate is 2-10 ℃/h, the initial temperature is 20 ℃ at room temperature, and the humidity is 80%; keeping the temperature and moisture at 60-80 deg.C and 40% humidity for 20-48 h;
and step six, calcining in a muffle furnace to obtain the high thermal shock resistance marine SCR denitration catalyst.
8. The preparation method of the SCR denitration catalyst for the honeycomb ship with the high thermal shock resistance as recited in claim 7, wherein in the first step, the preparation of an active precursor solution: dissolving ammonium metavanadate and cerium nitrate into deionized water, and adding an alkaline cosolvent to completely dissolve the ammonium metavanadate and the cerium nitrate to obtain the cerium nitrate;
wherein the mass ratio of ammonium metavanadate to cerium nitrate is 5-25: 1-10; the addition amount of the alkaline cosolvent is 0 to 10 weight parts.
9. The preparation method of the SCR denitration catalyst for the honeycomb ship with the high thermal shock resistance as defined in claim 7, wherein the denitration activity of the SCR catalyst is more than 80% after the SCR catalyst is subjected to thermal shock circulation at 550 ℃ for 30 times.
10. The preparation method of the SCR denitration catalyst for the honeycomb ship with the high thermal shock resistance according to claim 7, wherein the calcination process in the sixth step is as follows:
firstly, placing a dried sample in a muffle furnace, gradually heating the sample from room temperature to 200 ℃, wherein the heating rate is 1-10 ℃/min;
secondly, keeping the temperature at 200 ℃ for 3-6 h;
thirdly, gradually heating from 200 ℃ to 620 ℃, wherein the heating rate is 50-100 ℃/h, and then preserving heat for 3-12 h; fourthly, after the calcination is completed, the mixture is gradually cooled to the room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910917688.2A CN110639502A (en) | 2019-09-26 | 2019-09-26 | SCR denitration catalyst with high thermal shock resistance for honeycomb ship and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910917688.2A CN110639502A (en) | 2019-09-26 | 2019-09-26 | SCR denitration catalyst with high thermal shock resistance for honeycomb ship and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110639502A true CN110639502A (en) | 2020-01-03 |
Family
ID=68992854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910917688.2A Pending CN110639502A (en) | 2019-09-26 | 2019-09-26 | SCR denitration catalyst with high thermal shock resistance for honeycomb ship and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110639502A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672504A (en) * | 2020-06-03 | 2020-09-18 | 北京海顺德钛催化剂有限公司 | Catalyst for moving bed and/or fluidized bed denitration device and preparation method and application thereof |
| CN113769732A (en) * | 2021-09-16 | 2021-12-10 | 山东博霖环保科技发展有限公司 | Medium-temperature flue gas SCR denitration catalyst and preparation method thereof |
| CN114308012A (en) * | 2022-01-06 | 2022-04-12 | 浙江德创环保科技股份有限公司 | Preparation method of high-porosity denitration catalyst |
| CN114308013A (en) * | 2022-01-06 | 2022-04-12 | 浙江德创环保科技股份有限公司 | Production process of low-cost high-temperature denitration catalyst |
| CN115106130A (en) * | 2022-07-11 | 2022-09-27 | 南京赤博环保科技有限公司 | Process for preparing honeycomb denitration catalyst by using failed ceramic catalytic filter tube |
| CN115672382A (en) * | 2022-10-10 | 2023-02-03 | 中煤科工西安研究院(集团)有限公司 | Wide low-temperature honeycomb catalyst and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4852690A (en) * | 1971-11-05 | 1973-07-24 | ||
| KR860002129B1 (en) * | 1981-11-19 | 1986-12-11 | 사바쇼오이찌 | Catalyst carriers for purification of waste gas and process for preparing the same |
| CN1276260A (en) * | 1999-06-02 | 2000-12-13 | 中国科学院生态环境研究中心 | Cellular ceramics with low thermal expansibility |
| CN101062868A (en) * | 2007-04-11 | 2007-10-31 | 南京工业大学 | Multi-phase functional ceramic honeycomb support and preparation method thereof |
| CN102256912A (en) * | 2008-12-18 | 2011-11-23 | 陶氏环球技术有限责任公司 | Ceramic honeycomb filter with enhanced thermal shock resistance |
| CN102755898A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Semiconductor control rectifier (SCR) denitration catalytic agent applicable to high ash-laden gas condition and preparation method thereof |
| CN103861653A (en) * | 2012-12-14 | 2014-06-18 | 上海郎特电力环保科技有限公司 | Modified titanium dioxide, ultrafine crystal ceramic powder, high-strength heat-engine plant denitration catalyst, and preparation methods of modified titanium dioxide, ultrafine crystal ceramic powder, and high-strength heat-engine plant denitration catalyst |
| CN104190394A (en) * | 2014-09-19 | 2014-12-10 | 西南化工研究设计院有限公司 | Honeycombed denitration catalyst taking titanium aluminum composite oxide as carrier and preparation method thereof |
| CN107597095A (en) * | 2017-10-31 | 2018-01-19 | 湖北神雾热能技术有限公司 | A kind of rare-earth-based Integral forming type organic exhaust gas heat-storage catalytic honeycomb ceramics and its preparation technology |
| CN107694558A (en) * | 2017-09-30 | 2018-02-16 | 湖北神雾热能技术有限公司 | A kind of SCR catalyst for having denitration heat accumulation function concurrently and preparation method thereof |
-
2019
- 2019-09-26 CN CN201910917688.2A patent/CN110639502A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4852690A (en) * | 1971-11-05 | 1973-07-24 | ||
| KR860002129B1 (en) * | 1981-11-19 | 1986-12-11 | 사바쇼오이찌 | Catalyst carriers for purification of waste gas and process for preparing the same |
| CN1276260A (en) * | 1999-06-02 | 2000-12-13 | 中国科学院生态环境研究中心 | Cellular ceramics with low thermal expansibility |
| CN101062868A (en) * | 2007-04-11 | 2007-10-31 | 南京工业大学 | Multi-phase functional ceramic honeycomb support and preparation method thereof |
| CN102256912A (en) * | 2008-12-18 | 2011-11-23 | 陶氏环球技术有限责任公司 | Ceramic honeycomb filter with enhanced thermal shock resistance |
| CN102755898A (en) * | 2012-08-07 | 2012-10-31 | 江苏龙源催化剂有限公司 | Semiconductor control rectifier (SCR) denitration catalytic agent applicable to high ash-laden gas condition and preparation method thereof |
| CN103861653A (en) * | 2012-12-14 | 2014-06-18 | 上海郎特电力环保科技有限公司 | Modified titanium dioxide, ultrafine crystal ceramic powder, high-strength heat-engine plant denitration catalyst, and preparation methods of modified titanium dioxide, ultrafine crystal ceramic powder, and high-strength heat-engine plant denitration catalyst |
| CN104190394A (en) * | 2014-09-19 | 2014-12-10 | 西南化工研究设计院有限公司 | Honeycombed denitration catalyst taking titanium aluminum composite oxide as carrier and preparation method thereof |
| CN107694558A (en) * | 2017-09-30 | 2018-02-16 | 湖北神雾热能技术有限公司 | A kind of SCR catalyst for having denitration heat accumulation function concurrently and preparation method thereof |
| CN107597095A (en) * | 2017-10-31 | 2018-01-19 | 湖北神雾热能技术有限公司 | A kind of rare-earth-based Integral forming type organic exhaust gas heat-storage catalytic honeycomb ceramics and its preparation technology |
Non-Patent Citations (2)
| Title |
|---|
| MARIUS HACKEL ET AL.: ""Kinetics of reduction and oxidation reactions for application in catalytic gas–particle-filters"", 《POWDER TECHNOLOGY》 * |
| 支浩等: ""净化器载体在汽车尾气处理中的研究进展"", 《材料导报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672504A (en) * | 2020-06-03 | 2020-09-18 | 北京海顺德钛催化剂有限公司 | Catalyst for moving bed and/or fluidized bed denitration device and preparation method and application thereof |
| CN111672504B (en) * | 2020-06-03 | 2024-03-19 | 北京海顺德钛催化剂有限公司 | Catalyst for moving bed and/or fluidized bed denitration device and preparation method and application thereof |
| CN113769732A (en) * | 2021-09-16 | 2021-12-10 | 山东博霖环保科技发展有限公司 | Medium-temperature flue gas SCR denitration catalyst and preparation method thereof |
| CN114308012A (en) * | 2022-01-06 | 2022-04-12 | 浙江德创环保科技股份有限公司 | Preparation method of high-porosity denitration catalyst |
| CN114308013A (en) * | 2022-01-06 | 2022-04-12 | 浙江德创环保科技股份有限公司 | Production process of low-cost high-temperature denitration catalyst |
| CN115106130A (en) * | 2022-07-11 | 2022-09-27 | 南京赤博环保科技有限公司 | Process for preparing honeycomb denitration catalyst by using failed ceramic catalytic filter tube |
| CN115672382A (en) * | 2022-10-10 | 2023-02-03 | 中煤科工西安研究院(集团)有限公司 | Wide low-temperature honeycomb catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110639502A (en) | SCR denitration catalyst with high thermal shock resistance for honeycomb ship and preparation method thereof | |
| KR102643224B1 (en) | Supported catalyst, monolithic selective catalytic reduction (SCR) catalyst, method for producing the same, and method for removing nitrogen oxides | |
| CN103263912B (en) | Diesel vehicle tail gas purifying catalyst and preparation method thereof | |
| CN107824217B (en) | Preparation method of coating slurry and preparation method of coating type Cu molecular sieve SCR catalyst | |
| WO2015161627A1 (en) | Honeycomb denitration catalyst for flue gas at 400°c-600°c and preparation method therefor | |
| PL198392B1 (en) | Exhaust gas catalyst comprising rhodium, zirconia and rare earth oxide | |
| CN111167487B (en) | Multifunctional catalyst, preparation method and application thereof | |
| CN113289609B (en) | High-wear-resistance wide-temperature denitration catalyst and preparation method and application thereof | |
| CN105944718A (en) | Integral DOC catalyst for marine diesel engine tail gas purification and preparation process thereof | |
| CN111715302B (en) | Poisoning-resistant metal oxide denitration catalyst and preparation method thereof | |
| CN109225203A (en) | A kind of vanadium base oxide SCR catalyst preparation method and its catalyst of preparation | |
| CN113304745A (en) | Pt-Pd-Rh ternary catalyst and preparation method thereof | |
| CN108837829B (en) | Preparation method of layered three-way catalyst for natural gas vehicle | |
| CN112973668A (en) | High-strength honeycomb type low-temperature SCR denitration catalyst and preparation method thereof | |
| CN111330633B (en) | Diesel vehicle oxidation catalyst with low-temperature adsorption capacity and preparation method thereof | |
| KR100416735B1 (en) | Catalyst for purifying exhaust gas from car and method for preparing thereof | |
| US9669389B2 (en) | Carrier for internal-combustion engine exhaust gas purification catalyst | |
| CN115178292A (en) | High-sulfur-resistance molecular sieve-based monolithic SCR catalyst and preparation method thereof | |
| CN111266123A (en) | Multifunctional catalyst for purification and preparation method and application thereof | |
| CN116510745A (en) | Preparation method of catalyst for synergistic denitration and carbon monoxide removal | |
| CN115819107A (en) | Cordierite honeycomb ceramic carrier with low thermal expansion coefficient, preparation method and application | |
| KR20200034165A (en) | Diesel oxidation catalyst with excellent heat durability and Method thereof | |
| CN108311157A (en) | A kind of nanometer catalyst and preparation method thereof | |
| CN116139919A (en) | SCR catalyst and preparation method thereof | |
| WO2021198650A1 (en) | Novel tin incorporated catalysts for gasoline engine exhaust gas treatments |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: No.557 Qianhu Road, Qianqiao Town, Wuxi City, Jiangsu Province Applicant after: JIANGSU LONGYUAN CATALYST Co.,Ltd. Applicant after: BEIJING GUODIAN LONGYUAN ENVIRONMENTAL ENGINEERING Co.,Ltd. Address before: 100039, room 1, building 16, No. 911 West Fourth Ring Road, Beijing, Haidian District Applicant before: BEIJING GUODIAN LONGYUAN ENVIRONMENTAL ENGINEERING Co.,Ltd. Applicant before: JIANGSU LONGYUAN CATALYST Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200103 |