CN106475128A - A kind of preparation method of industrial waste gas purifying catalyst - Google Patents
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
The invention provides a kind of preparation method of industrial waste gas purifying catalyst, it is possible to increase the anti-sintering property of catalyst, and improve catalysis activity, comprise the following steps：1) by aluminum isopropylate., and one or more of alkaline earth precursor, rare earth precursor, transition metal precursor, it is dissolved in solvent；2) add activated alumina, silicon nitride, dispersant, stirring mixing, form suspension slurry；3) coating forms catalyst coatings on a catalyst support, is dried；4) it is placed in roasting in the reducing atmosphere of flowing；5) immerse noble metal solution impregnated, be dried, roasting, sintering temperature is 400～700 DEG C, form final products.
Description
【Technical field】
The present invention relates to waste gas purification field, more particularly, to a kind of industrial waste gas purifying catalyst and preparation method thereof.
【Background technology】
It is known that industrial waste gas (as volatile organic matter (VOCs) etc.) and vehicle exhaust are (as carbon monoxide, hydrocarbonization
Compound and nitrogen oxides etc.) be atmosphere pollution main source.Motor-vehicle tail-gas due to three-way catalyst development and application
Substantially it is purified, VOCs becomes and causes one of main factor of atmospheric pollution.From chemical industry, electron trade, printer
Industry, paint and the industrial process such as coating, boiler of power plant tail gas and construction material, finishing material, the adhesive of furniture, kitchen oil
The Organic substance of the daily life such as cigarette discharge is (as lower carbon number hydrocarbons, aromatic hydrocarbons, alcohol, ketone, ether, ester, aldehyde, carboxylic acid, amine and halogen-containing and sulfur-bearing
Organic substance etc.) overwhelming majority has toxicity, foul smell and inflammable and explosive, and VOCs is also possible to generate toxicity bigger after entering air
Photochemical fog.Because VOCs pollution is wide, harm is big, complicated, difficulty of governance are big, the control of research VOCs and improvement are right
Significant in human social.Become environmental catalysis field one grinds the purification treatment technology of VOCs
Study carefully focus.
At present, catalysis method be acknowledged as most effective and have huge applications prospect thorough elimination VOCs means it
One.In catalysis burn processing VOCs waste gas technology, the quality of catalyst has decisive influence to treatment effeciency and energy consumption.Cause
This finds the catalyst always study hotspot of low-temperature catalytic oxidation VOCs of high activity, high thermal stability.Traditional catalyst
There are noble metal catalyst and transition-metal catalyst.Carried noble metal (Pd, Pt, Ag etc.) catalyst has good low temperature and lives
Property, but it is expensive, and active component is volatile, sintering and being poisoned.With low cost, the master of catalyst of transition metal oxide
It is used for middle temperature catalysis oxidation, but its anti-poisoning and sintering character are poor.Common oxide and perovskite structure composite oxygen
Compound catalyst equally exists the defect of easy-sintering inactivation.
【Content of the invention】
Object of the present invention is to provide a kind of preparation method of industrial waste gas purifying catalyst, it is possible to increase catalyst
Anti-sintering property, and improve catalysis activity.
The technical scheme is that：
A kind of preparation method of industrial waste gas purifying catalyst is it is characterised in that comprise the following steps：
1) by aluminum isopropylate., and one of alkaline earth precursor, rare earth precursor, transition metal precursor
Or several, it is dissolved in solvent, obtain slaine precursor solution；
2) in step 1) the slaine precursor solution that obtains adds activated alumina, silicon nitride, dispersant, and stirring is mixed
Close, form suspension slurry；
3) by step 2) coating of the suspension slurry that obtains forms catalyst coatings on a catalyst support, it is dried to water content
Less than or equal to 3%, obtain presoma is dried；
4) by step 3) presoma that is dried that obtains is placed in roasting in the reducing atmosphere of flowing, roasts at 500～600 DEG C
Burn 0.5～2h, in 1000～1400 DEG C of roasting 2～6h, obtain pretreatment body；
5) by step 4) the pretreatment body that obtains immerses in the precious metal solution of 0.01～0.3mol/L, dipping 5～
10min, is dried, roasting, and sintering temperature is 400～700 DEG C, forms final products.
Further, above-mentioned steps 1) in alkaline earth precursor be barium nitrate, barium acetate, strontium nitrate, calcium nitrate, vinegar
Sour magnesium or magnesium nitrate；Rare earth precursor is Lanthanum (III) nitrate, lanthanum acetate, cerous nitrate, cerous acetate, Yttrium trinitrate, acetic acid yttrium；Transition gold
Genus predecessor is manganese nitrate, manganese acetate, cobalt nitrate, cobaltous acetate, ferric nitrate, iron acetate, iron chloride.
Further, alkaline-earth metal in above-mentioned slaine precursor solution, rare earth metal, transition metal ionss concentration it
With for 0.01～0.1mol/L, the addition of aluminum isopropylate. is alkaline-earth metal, the molal quantity of rare earth metal, transition metal ionss is total
With.
Further, above-mentioned steps 2) in silicon nitride be α-siliconnitride or nm amorphous silicon nitride.α-siliconnitride or
The reactivity of nm amorphous silicon nitride is high, is conducive to improving the substitution amount to Al-O key for the Si-N key.
Further, above-mentioned steps 2) in the addition of silicon nitride be 0.9～1.1 times of aluminum isopropylate. molal quantity, live
Property aluminium oxide addition be alkaline-earth metal, rare earth metal, 9.5～10.5 times of the molal quantity summation of transition metal ionss.
Further, above-mentioned steps 2) in dispersant be sodium polyacrylate, polycarboxylic acids sodium or phenylethylene-maleic anhydride altogether
Polymers, naphthalenesulfonate antiprecipitant one or more.Dispersant makes suspension stably not precipitate, and is conducive to carrying of uniformity
High.
Further, the addition of above-mentioned dispersant is the 0.1～1% of activated alumina and silicon nitride powder weight.
Further, above-mentioned steps 3) drying be lyophilization, pressure be 10～40Pa.Lyophilization is to utilize moisture
Distillation does not reach dry purpose, and dried small product size is constant, loose porous, easy to crack or come off.
Further, above-mentioned steps 3) in catalyst coatings thickness be 0.2～2 μm.
Further, above-mentioned steps 5) precious metal solution in the sodium citrate containing 0.01～0.3mol/L or citric acid
Potassium or potassium acetate or Disodium oxalate..
The present invention can produce following beneficial technique effect：
(1) catalyst of present invention preparation is that (chemical formula is the hexa-aluminate that replaced by Si-N key of part Al-O key
AAl12O19, A is metal) and noble metal composite catalyst；Si-N key and Al-O key have close bond distance and bond energy, therefore Si-
N key can replace the part Al-O key in hexa-aluminate structure and maintain Stability Analysis of Structures constant, but, the introducing of Si-N key can increase
Plus the Lacking oxygen defect of hexa-aluminate structure, for the absorption substantial amounts of active sites of offer of gas phase oxygen molecule, increase surface adsorption anti-
Should, improve catalysis activity；Meanwhile, the Lacking oxygen uniformly existing in structure is also beneficial to improve the expansion in lattice of atom or ion
Scattered speed, improves the reactivity of Lattice Oxygen further, greatly improves rate of catalysis reaction, improves catalysis activity.
(2) the catalyst Si-N key of present invention preparation replaces the part Al-O key in hexa-aluminate structure, due to Si-N key
Bond energy be greater than the bond energy of Al-O key, therefore, to carried metal to contain overall steadiness higher, can be by carried metal bundle
It is tied in certain space, substantially reduce various loaded noble metal catalysts and be derived from the sintering of carrier itself in practicality and lead
The catalyst deactivation causing, improves the anti-sintering property of catalyst.
(3) present invention adopts activated alumina and aluminum isopropylate. as the silicon source forming hexa-aluminate structure, using isopropyl
Aluminium alcoholates is decomposed to form porous network shape aluminum, itself and other reacted constituents can be made to be dispersed in wherein, increase the uniform of structure
Property, the especially Si-N key replacement adding generation of silicon nitride, substitution amount is high, product good crystallinity, using partly low cost
Activated alumina can be suitable reduces cost, integrated cost and effect.
(4) present invention adopts lyophilization and unconventional heat drying, reaches dry purpose using water sublimed, does
Small product size after dry is constant, loose porous, even if adding additives or surface modifier are not easy to ftracture or come off, Neng Gouti
Uniformity on atomic level for the high catalyst activity site, improves catalysis activity, reduces active layer thickness, reduces consumption.
(5) present invention first time roasting, using the reducing atmosphere of flowing, ensure that Si-N key is successfully entered six aluminic acids
The structure of salt and not oxidized, the N/O ratio of product maintains more than 5%, once and Si-N key enter define hexa-aluminate
Crystal structure, then sufficiently stable, all without oxidized in follow-up after baking and high temperature real-world environment, maintain stable and
Effectively it is catalyzed.
【Specific embodiment】
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment provided below simultaneously is not used to limit the scope that the present invention is covered, and described step is not to use
To limit its execution sequence.Those skilled in the art do conspicuously improved with reference to existing common knowledge to the present invention, also fall
Enter within the protection domain of application claims.
Embodiment one
A kind of preparation method of industrial waste gas purifying catalyst is it is characterised in that comprise the following steps：
1) will be soluble in water to aluminum isopropylate., strontium nitrate, cerous nitrate, obtaining Al concentration for 0.02mol/L, Sr concentration is
0.01mol/L, Ce concentration is the slaine precursor solution of 0.01mol/L；
In step 1) the slaine precursor solution that obtains adds activated alumina, silicon nitride, dispersant sodium polyacrylate,
The addition of silicon nitride is 0.9～1.1 times of aluminum isopropylate. molal quantity, the addition of activated alumina be Sr and Ce mole
9.5～10.5 times of number summation, the addition of dispersant sodium polyacrylate is the 0.1 of activated alumina and silicon nitride powder weight
～1%, stirring mixing, form suspension slurry；
2) by step 2) coating of the suspension slurry that obtains forms the coating of catalysis 0.2～2 μ m-thick on a catalyst support,
Lyophilization, pressure is 10～40Pa, until water content is less than or equal to 3%, obtains presoma is dried；
3) by step 3) presoma that is dried that obtains is placed in roasting in the nitrogen atmosphere of flowing, roasting at 500～600 DEG C
0.5～2h, in 1000～1400 DEG C of roasting 2～6h, obtains pretreatment body；
4) by step 4) the pretreatment body that obtains immerses in the precious metal solution of 0.01～0.3mol/L, this precious metal solution
In the sodium citrate containing 0.01～0.3mol/L, impregnate 5～10min, be dried, roasting, sintering temperature be 400～700 DEG C, shape
Become final products.
After testing, the N/O in catalyst, than for 6.3%, illustrates that Si-N key is stable in the presence of in structure；By this catalyst extremely
In internal diameter in the reaction tube of 6mm, with dimethylbenzene, toluene and phenyl methylcarbamate for organic contamination source, adjust respectively dimethylbenzene, toluene and
The carrier gas flux of phenyl methylcarbamate place gas circuit is so as to concentration respectively reaches 1000mg/m3、3000mg/m3、5000mg/m3, react wet
Spend for 30%RH, in reaction, air mixed gas flow is 300ml/min, is that reaction velocity reaches 110000h-1.Result shows, urges
Above-mentioned waste gas complete catalysts oxidation can be carbon dioxide and water in 600 DEG C by agent；Under identical test environment, pass through
300 DEG C, 600h stability test, substantially inactivating does not occur in catalyst.
Embodiment two
A kind of preparation method of industrial waste gas purifying catalyst is it is characterised in that comprise the following steps：
1) will be soluble in water to aluminum isopropylate., manganese nitrate, acetic acid yttrium, obtaining Al concentration for 0.05mol/L, Mn concentration is
0.02mol/L, Y concentration is the slaine precursor solution of 0.03mol/L；
2) in step 1) the slaine precursor solution that obtains adds activated alumina, nano-silicon nitride, the poly- carboxylic of dispersant
Sour sodium, the addition of silicon nitride is 0.9～1.1 times of aluminum isopropylate. molal quantity, and the addition of activated alumina is rubbing of Mn and Y
9.5～10.5 times of that number summation, the addition of dispersant polycarboxylic acids sodium is activated alumina and Nano powder of silicon nitride quality
0.1～1%, stirring mixing, formed suspension slurry；
3) by step 2) coating of the suspension slurry that obtains forms the coating of catalysis 0.2～2 μ m-thick on a catalyst support,
Lyophilization, pressure is 10～40Pa, until water content is less than or equal to 3%, obtains presoma is dried；
4) by step 3) presoma that is dried that obtains is placed in roasting in the nitrogen atmosphere of flowing, roasting at 500～600 DEG C
0.5～2h, in 1000～1400 DEG C of roasting 2～6h, obtains pretreatment body；
5) by step 4) the pretreatment body that obtains immerses in the precious metal solution of 0.01～0.3mol/L, this precious metal solution
In the potassium citrate containing 0.01～0.3mol/L, impregnate 5～10min, be dried, roasting, sintering temperature be 400～700 DEG C, shape
Become final products.
After testing, the N/O in catalyst, than for 6.9%, illustrates that Si-N key is stable in the presence of in structure；By this catalyst extremely
In internal diameter in the reaction tube of 6mm, with dimethylbenzene, toluene and phenyl methylcarbamate for organic contamination source, adjust respectively dimethylbenzene, toluene and
The carrier gas flux of phenyl methylcarbamate place gas circuit is so as to concentration respectively reaches 1000mg/m3、3000mg/m3、5000mg/m3, react wet
Spend for 30%RH, in reaction, air mixed gas flow is 300ml/min, is that reaction velocity reaches 110000h-1.Result shows, urges
Above-mentioned waste gas complete catalysts oxidation can be carbon dioxide and water in 600 DEG C by agent；Under identical test environment, pass through
300 DEG C, 300h stability test, substantially inactivating does not occur in catalyst.
Embodiment three
A kind of preparation method of industrial waste gas purifying catalyst is it is characterised in that comprise the following steps：
1) will be soluble in water to aluminum isopropylate., calcium nitrate, cobaltous acetate, Lanthanum (III) nitrate, obtaining Al concentration is 0.1mol/L, Ca concentration
It is the slaine precursor solution that 0.04mol/L, La concentration is 0.04mol/L for 0.02mol/L, Co concentration；
2) in step 1) the slaine precursor solution that obtains adds activated alumina, α-siliconnitride, dispersant LOMAR PWA EINECS 246-676-2
Salt antiprecipitant, the addition of silicon nitride is 0.9～1.1 times of aluminum isopropylate. molal quantity, and the addition of activated alumina is
9.5～10.5 times of the molal quantity summation of Ca, Co, La, the addition of dispersant naphthalenesulfonate antiprecipitant is active oxidation
Aluminum and the 0.1～1% of silicon nitride powder weight, stirring mixing, form suspension slurry；
3) by step 2) coating of the suspension slurry that obtains forms the coating of catalysis 0.2～2 μ m-thick on a catalyst support,
Lyophilization, pressure is 10～40Pa, until water content is less than or equal to 3%, obtains presoma is dried；
4) by step 3) presoma that is dried that obtains is placed in roasting in the nitrogen atmosphere of flowing, roasting at 500～600 DEG C
0.5～2h, in 1000～1400 DEG C of roasting 2～6h, obtains pretreatment body；
5) by step 4) the pretreatment body that obtains immerses in the precious metal solution of 0.01～0.3mol/L, this precious metal solution
In the potassium acetate containing 0.01～0.3mol/L, impregnate 5～10min, be dried, roasting, sintering temperature be 400～700 DEG C, formed
Final products.
After testing, the N/O in catalyst, than for 7.1%, illustrates that Si-N key is stable in the presence of in structure；By this catalyst extremely
In internal diameter in the reaction tube of 6mm, with dimethylbenzene, toluene and phenyl methylcarbamate for organic contamination source, adjust respectively dimethylbenzene, toluene and
The carrier gas flux of phenyl methylcarbamate place gas circuit is so as to concentration respectively reaches 1000mg/m3、3000mg/m3、5000mg/m3, react wet
Spend for 30%RH, in reaction, air mixed gas flow is 300ml/min, is that reaction velocity reaches 110000h-1.Result shows, urges
Above-mentioned waste gas complete catalysts oxidation can be carbon dioxide and water in 600 DEG C by agent；Under identical test environment, pass through
300 DEG C, 300h stability test, substantially inactivating does not occur in catalyst.
Example IV
A kind of preparation method of industrial waste gas purifying catalyst is it is characterised in that comprise the following steps：
1) will be soluble in water to aluminum isopropylate., barium nitrate, iron chloride, obtaining Al concentration is 0.01～0.1mol/L, Ba concentration
The slaine precursor solution being 0.01～0.1mol/L for 0.01～0.1mol/L, Fe concentration；
2) in step 1) the slaine precursor solution that obtains adds activated alumina, silicon nitride, dispersant styrene-horse
Carry out acid anhydride copolymer, the addition of silicon nitride is 0.9～1.1 times of aluminum isopropylate. molal quantity, the addition of activated alumina is
9.5～10.5 times of the molal quantity summation of Ba and Fe, the addition of dispersant styrene-maleic anhydride copolymer is active oxidation
Aluminum and the 0.1～1% of silicon nitride powder weight, stirring mixing, form suspension slurry；
3) by step 2) coating of the suspension slurry that obtains forms the coating of catalysis 0.2～2 μ m-thick on a catalyst support,
Lyophilization, pressure is 10～40Pa, until water content is less than or equal to 3%, obtains presoma is dried；
4) by step 3) presoma that is dried that obtains is placed in roasting in the nitrogen atmosphere of flowing, roasting at 500～600 DEG C
0.5～2h, in 1000～1400 DEG C of roasting 2～6h, obtains pretreatment body；
5) by step 4) the pretreatment body that obtains immerses in the precious metal solution of 0.01～0.3mol/L, this precious metal solution
In the Disodium oxalate. containing 0.01～0.3mol/L, impregnate 5～10min, be dried, roasting, sintering temperature be 400～700 DEG C, formed
Final products.
After testing, the N/O in catalyst, than for 6.8%, illustrates that Si-N key is stable in the presence of in structure；By this catalyst extremely
In internal diameter in the reaction tube of 6mm, with dimethylbenzene, toluene and phenyl methylcarbamate for organic contamination source, adjust respectively dimethylbenzene, toluene and
The carrier gas flux of phenyl methylcarbamate place gas circuit is so as to concentration respectively reaches 1000mg/m3、3000mg/m3、5000mg/m3, react wet
Spend for 30%RH, in reaction, air mixed gas flow is 300ml/min, is that reaction velocity reaches 110000h-1.Result shows, urges
Above-mentioned waste gas complete catalysts oxidation can be carbon dioxide and water in 600 DEG C by agent；Under identical test environment, pass through
300 DEG C, 300h stability test, substantially inactivating does not occur in catalyst.
Claims (10)
1. a kind of preparation method of industrial waste gas purifying catalyst is it is characterised in that comprise the following steps：
1) by aluminum isopropylate., and one of alkaline earth precursor, rare earth precursor, transition metal precursor or several
Kind, it is dissolved in solvent, obtain slaine precursor solution；
2) in step 1) the slaine precursor solution that obtains adds activated alumina, silicon nitride, dispersant, stirring mixing, shape
Become suspension slurry；
3) by step 2) coating of the suspension slurry that obtains forms catalysis catalyst coatings on a catalyst support, it is dried to water content
Less than or equal to 3%, obtain presoma is dried；
4) by step 3) presoma that is dried that obtains is placed in roasting in the reducing atmosphere of flowing, roasting at 500～600 DEG C
0.5～2h, in 1000～1400 DEG C of roasting 2～6h, obtains pretreatment body；
5) by step 4) the pretreatment body that obtains immerses in the precious metal solution of 0.01～0.3mol/L, impregnates 5～10min, do
Dry, roasting, sintering temperature is 400～700 DEG C, forms final products.
2. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described step 1) in
Alkaline earth precursor be barium nitrate, barium acetate, strontium nitrate, calcium nitrate, magnesium acetate or magnesium nitrate；Rare earth precursor is
Lanthanum (III) nitrate, lanthanum acetate, cerous nitrate, cerous acetate, Yttrium trinitrate, acetic acid yttrium；Transition metal predecessor is manganese nitrate, manganese acetate, nitric acid
Cobalt, cobaltous acetate, ferric nitrate, iron acetate, iron chloride.
3. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described slaine
In precursor solution, alkaline-earth metal, rare earth metal, the concentration sum of transition metal ionss are 0.01～0.1mol/L, aluminum isopropylate.
Addition be alkaline-earth metal, rare earth metal, the molal quantity summation of transition metal ionss.
4. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described step 2)
In silicon nitride be α-siliconnitride or nm amorphous silicon nitride.
5. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described step 2)
In the addition of silicon nitride be 0.9～1.1 times of aluminum isopropylate. molal quantity, the addition of activated alumina is alkaline-earth metal,
Rare earth metal, 9.5～10.5 times of the molal quantity summation of transition metal ionss.
6. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described step 2)
In dispersant be sodium polyacrylate, polycarboxylic acids sodium or styrene-maleic anhydride copolymer, the one of naphthalenesulfonate antiprecipitant
Plant or several.
7. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described dispersant
Addition be the 0.1～1% of activated alumina and silicon nitride powder weight.
8. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described step 3)
Drying be lyophilization, pressure be 10～40Pa.
9. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described step 3)
In catalyst coatings thickness be 0.2～2 μm.
10. the preparation method of industrial waste gas purifying catalyst according to claim 1 is it is characterised in that described step
5) sodium citrate containing 0.01～0.3mol/L or potassium citrate or potassium acetate or Disodium oxalate. in precious metal solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109999657A (en) * | 2019-05-08 | 2019-07-12 | 苏州绿锦一方环保科技发展有限公司 | A kind of method of multistage purification processing exhaust gas |
| CN110841891A (en) * | 2019-11-15 | 2020-02-28 | 一汽解放汽车有限公司 | Coating method for stabilizing catalytic performance of wall-flow type particle filter catalytic coating by adopting polyelectrolyte |
| CN111841317A (en) * | 2019-12-12 | 2020-10-30 | 万华化学集团股份有限公司 | Phosgene decomposition structured packing catalyst, preparation method thereof, phosgene-containing tail gas treatment device and treatment method |
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| CN104781004A (en) * | 2012-12-27 | 2015-07-15 | 三井金属矿业株式会社 | Catalyst carrier and exhaust gas purifying catalyst |
| CN105289676A (en) * | 2015-10-27 | 2016-02-03 | 展宗城 | Foam-like low-temperature SCR catalyst and preparation method thereof |
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| CN1346694A (en) * | 2000-09-29 | 2002-05-01 | 株式会社电装 | Ceramic catalyst body and ceramic carrier |
| US20140147358A1 (en) * | 2012-11-12 | 2014-05-29 | Basf Se | Oxidation Catalyst And Method For Its Preparation |
| CN104781004A (en) * | 2012-12-27 | 2015-07-15 | 三井金属矿业株式会社 | Catalyst carrier and exhaust gas purifying catalyst |
| CN105289676A (en) * | 2015-10-27 | 2016-02-03 | 展宗城 | Foam-like low-temperature SCR catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109999657A (en) * | 2019-05-08 | 2019-07-12 | 苏州绿锦一方环保科技发展有限公司 | A kind of method of multistage purification processing exhaust gas |
| CN109999657B (en) * | 2019-05-08 | 2021-06-22 | 苏州绿锦一方环保科技发展有限公司 | Method for multi-stage purification treatment of waste gas |
| CN110841891A (en) * | 2019-11-15 | 2020-02-28 | 一汽解放汽车有限公司 | Coating method for stabilizing catalytic performance of wall-flow type particle filter catalytic coating by adopting polyelectrolyte |
| CN111841317A (en) * | 2019-12-12 | 2020-10-30 | 万华化学集团股份有限公司 | Phosgene decomposition structured packing catalyst, preparation method thereof, phosgene-containing tail gas treatment device and treatment method |
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