CN102000600B - Integral normal-temperature micro nitrogen oxide purification material and preparation method thereof - Google Patents
Integral normal-temperature micro nitrogen oxide purification material and preparation method thereof Download PDFInfo
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- CN102000600B CN102000600B CN2010105476957A CN201010547695A CN102000600B CN 102000600 B CN102000600 B CN 102000600B CN 2010105476957 A CN2010105476957 A CN 2010105476957A CN 201010547695 A CN201010547695 A CN 201010547695A CN 102000600 B CN102000600 B CN 102000600B
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Abstract
The invention discloses an integral normal-temperature micro nitrogen oxide purification material using a nanometer transition metal oxide modified molecular sieve. The purification material is prepared by high-temperature roasting, wherein the cordierite honeycomb ceramics is used as carrier, and the mixture of the nanometer transition metal oxide modified molecular sieve and gamma-A12O3 is used as active coating. The material comprises the following constituents in mass percentage: 20-80% of nanometer transition metal oxide modified molecular sieve, 18-78% of gamma-A12O3, and 2% of additive. The purification material of the invention has the advantages of high NOx purification efficiency, low cost, simple preparation process and the like in normal-temperature condition and can purify 60-95% of the NOx when the content of NOx is less than or equal to 20 ppm.
Description
Technical field
The present invention relates to the scavenging material in a kind of depollution of environment field and preparation method thereof, specifically is a kind of monoblock type normal temperature trace nitrogen oxide scavenging material that utilizes the nano transition metal oxides modified molecular screen and preparation method thereof.
Background technology
Nitrogen oxide (NOx) is one of major pollutants that cause photochemical fog and acid rain, and ecological environment and human health are had very big harm.Wherein NO can combine to make the people to poison NO with the hemoglobin in the blood
2Under solar radiation, playing the toxic smog that photochemical reaction forms with oxygen can stimulate people's eyes, schneiderian membrane, thereby causes pathology.Along with the fast development of industry, the processing of nitrogen oxide has been become the important subject of environmental area.The method of handling nitrogen oxide at present mainly contains catalytic reduction method (SCR), liquid absorption method, absorption method, plasma-activated method, microbial method etc.
Since the Cu-ZSM-5 of discovery Cu molecular sieve series such as Iwamoto in 1986 especially ion-exchange preparation NO is directly decomposed have advantages of high catalytic activity after; People have begun the broad research to molecular sieve catalysts, mainly concentrate in the research that contains base metal and noble metal two molecular sieve analog system materials.Molecular sieve is a kind of microporous crystalline silico aluminate with skeleton structure; Its hole diameter is even; Have bigger surface area, pore volume and stronger electrostatic field, the Molecular Adsorption littler than its diameter can be arrived the inside of vestibule in these holes, and polar molecule and saturated molecule are had the preferential adsorption ability; Have the adsorption capacity height, heat endurance waits the unexistent advantage of other adsorbent by force.What research was more at present is the modified molecular screen class scavenging material through the ion-exchange preparation.Though adsorption capacity and the activity of molecular sieve behind ion-exchanged all has raising, such catalyst need be under higher temperature competence exertion active, be not suitable under the normal temperature condition purified treatment to nitrogen oxide.
Retrieval through to prior art is found; Chinese patent CN1401412A discloses a kind of catalyst that is specifically designed to diesel vehicle and lean-burn gasoline motorcycle tail gas purification of nitrogen oxides; Its developed by molecule formula is Fe-Mo/ZSM-5; This catalyst all reaches more than 96% the NO conversion ratio in the time of 400 ℃, in 300 ℃ of temperature ranges～all have more than 550 ℃ advantages of high catalytic activity.Though this catalyst has higher catalytic conversion to NO, it only just has catalytic action preferably under hot conditions, be not suitable for the purification of ambient temperature nitrogen oxide.
Find by retrieval again; Chinese patent CN101326004A discloses a kind of ambient temperature nitrogen oxide adsorbent; Oxide with at least a Co of being selected from, Cu, Mn, Fe, Ce element and two or more element combinations thereof is a carrier, and a kind of metal that load contains among Ag and the Pd at least is that active component is prepared from.In normal temperature atmosphere, do not exist under the situation of oxygen, this adsorbent can adsorb the NOx of capacity.But the adsorbent of this method preparation need comprise a kind of among Ag or the Pd at least, and cost is higher, and this adsorbent need use under the condition of anaerobic simultaneously, has also limited its range of application.
Summary of the invention
One of the object of the invention is the deficiency to prior art, and a kind of monoblock type normal temperature trace nitrogen oxide scavenging material is provided.
Two of the object of the invention is to provide the preparation method of this scavenging material.
For achieving the above object, the present invention adopts following technical scheme:
A kind of monoblock type normal temperature trace nitrogen oxide scavenging material is characterized in that this scavenging material is is carrier with the cordierite honeycomb ceramic, through molecular sieve, the γ～Al of nano transition metal oxides modification
2O
3The composite material that composite material and additive are formed is an active coating, makes through roasting; Wherein the mass ratio of cordierite honeycomb ceramic and active coating is 10:1～20:7; The composition of described active coating and mass percent are:
Molecular sieve powder 20～80% after the nano transition metal oxides modification;
γ～Al
2O
3 18～78%；
Additive 2%;
The content of nano transition metal oxides is 1～8% of molecular sieve weight in the said modified molecular screen;
The concrete steps of the molecular sieve powder of above-mentioned nano transition metal oxides modification are: transition metal nitrate is dissolved in the aqueous solution of polyvinylpyrrolidone that molecular weight is 10000 0.005mol/L; Dropwise add ammoniacal liquor in the stirring, be converted into the hydroxide of transition metal to transition metal nitrate fully; Continue to stir 1h, ageing 2～6 hours obtains the hydroxide sol of nano level transition metal; Molecular sieve is mixed in the colloidal sol to continue to stir makes its even dispersion; After filtration, washing, drying,, promptly get the molecular sieve of nano transition metal oxides modification 250～450 ℃ of roastings 2～4 hours.
Above-mentioned transition metal nitrate has: at least a nitrate in copper, manganese, cobalt, chromium, the iron.
Above-mentioned molecular sieve is 5A molecular sieve or 13X molecular sieve.
A kind of method for preparing above-mentioned monoblock type normal temperature trace nitrogen oxide scavenging material is characterized in that the concrete steps of this method are: with the molecular sieve powder after the modification and γ～Al
2O
3, additive is dissolved in the deionized water after the mixing and stirring, is prepared into slurry; Use HNO
3Regulating this slurry pH value is 2.5～4, makes coating paste, and slurry viscosity is 0.85～9.5mPas; Cordierite honeycomb ceramic carrier impregnated in the slurry 1～10 minute, take out the back and remove redundant sizing agent in the duct, dried 1～8 hour for 120 ℃; The oven dry back promptly makes this monoblock type normal temperature trace nitrogen oxide scavenging material 500～600 ℃ of roastings 2～6 hours, and it is 10～35% that active coating is uploaded rate.
Above-mentioned additive is one or more in ethylene glycol, isopropyl alcohol, glycerine and the polyethylene glycol.
The present invention utilizes the monoblock type normal temperature trace nitrogen oxide scavenging material of nano transition metal oxides modified molecular screen; This material has characteristics such as high to the NOx purification efficiency, that cost is low, preparation technology is simple, and relatively loose powder shape or the loading and unloading of granular adsorbent and carrying get up convenient relatively.
The monoblock type normal temperature trace nitrogen oxide scavenging material that utilizes the nano transition metal oxides modified molecular screen provided by the invention during NOx content≤20pppm, can reach 60～95% to the purification efficiency of NOx under normal temperature condition.
Scavenging material performance evaluation is carried out in Φ 16mm, the straight type glass tube of long 300mm reactor, and reaction gas volume air speed (GHSV) is 10000～20000 h
-1, be reflected under the normal temperature and pressure environment and carry out.Unstripped gas NOx concentration 4ppm, NO and NO
2Ratio is about 9:1, and all the other are air.
The specific embodiment
Elaborate in the face of embodiments of the invention down: present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Comparative Examples 1: take by weighing 4g5A molecular sieve and 1.15g boehmite, the 0.1g glycerine is mixed in the 8g deionized water, stirs 0.5h, uses HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 14.35% that this scavenging material active coating is uploaded rate.
The scavenging material that this Comparative Examples makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 43% to the purification efficiency of NOx.
Comparative Examples 2: take by weighing 4g13X molecular sieve and 1.15g boehmite, the 0.1g glycerine is mixed in the 8g deionized water, stirs 0.5h, uses HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 15.02% that this scavenging material active coating is uploaded rate.
The scavenging material that this Comparative Examples makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 32% to the purification efficiency of NOx.
Embodiment 1: with 0.15gCu (NO
3)
23H
2O is dissolved in polyvinylpyrrolidone (molecular weight the is 10000) aqueous solution of 50ml0.005mol/L, dropwise adds the ammoniacal liquor of 12.5ml0.1mol/L in the whipping process, continues to stir 1h, and ageing 2h makes nano level Cu (OH)
2Colloidal sol; The 5g5A molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make the 5A molecular sieve of modification again at 400 ℃ of following roasting 2h, and wherein the content of nanometer CuO is 1%.
The 5A molecular sieve, 1.15g boehmite, the 0.1g glycerine that take by weighing after the 4g modification are mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 15.13% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 65% to the purification efficiency of NOx.
Embodiment 2: with 0.2gMn (NO
3)
2The polyvinylpyrrolidone of solution and 50ml0.005mol/L (molecular weight is 10000) aqueous solution dropwise adds the ammoniacal liquor of 11.5ml0.1mol/L in the whipping process, continue to stir 1h, and ageing 2h makes nano level Mn (OH)
2Colloidal sol; The 5g5A molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make the 5A molecular sieve of modification, wherein nanometer MnO again at 400 ℃ of following roasting 2h
2Content be 1%.
The 5A molecular sieve, 1.15g boehmite, the 0.1g glycerine that take by weighing after the 4g modification are mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 15.94% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 72% to the purification efficiency of NOx.
Embodiment 3: with 0.18gCo (NO
3)
26H
2O is dissolved in polyvinylpyrrolidone (molecular weight the is 10000) aqueous solution of 50ml0.005mol/L, dropwise adds the ammoniacal liquor of 6ml0.1mol/L in the whipping process, continues to stir 1h, and ageing 2h makes nano level Co (OH)
2Colloidal sol; The 5g5A molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make the 5A molecular sieve of modification, wherein nano Co again at 400 ℃ of following roasting 2h
2O
3Content be 1%.
The 5A molecular sieve, 1.15g boehmite, the 0.1g glycerine that take by weighing after the 4g modification are mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 16.37% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 63% to the purification efficiency of NOx.
Embodiment 4: with 1.03gMn (NO
3)
2The polyvinylpyrrolidone of solution and 50ml0.005mol/L (molecular weight is 10000) aqueous solution dropwise adds the ammoniacal liquor of 57.5ml0.1mol/L in the whipping process, continue to stir 1h, and ageing 2h makes nano level Mn (OH)
2Colloidal sol; The 5g5A molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make the 5A molecular sieve of modification, wherein nanometer MnO again at 400 ℃ of following roasting 2h
2Content be 5%.
The 5A molecular sieve, 1.15g boehmite, the 0.1g glycerine that take by weighing after the 4g modification are mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 16.25% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 75% to the purification efficiency of NOx.
Embodiment 5: the 5A molecular sieve, 5g boehmite, the 0.1g glycerine that take by weighing after the modification of 1g embodiment 4 preparation are mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 18.25% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 55% to the purification efficiency of NOx.
Embodiment 6: with the Mn (NO of 1.03g
3)
2Solution and 0.45gCu (NO
3)
23H
2O is mixed in polyvinylpyrrolidone (molecular weight the is 10000) aqueous solution of 50ml0.005mol/L, dropwise adds the ammoniacal liquor of 95ml0.1mol/L in the whipping process, continues to stir 1h, and ageing 2h makes nano level Cu (OH)
2And Mn (OH)
2Colloidal sol; The 5g5A molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make modification 5A molecular sieve at 400 ℃ of following roasting 2h again, and wherein the content of nanometer CuO is 3%, nanometer MnO
2Content be 5%.
The 5A molecular sieve, 1.15g boehmite, the 0.1g glycerine that take by weighing after the 4g modification are mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 18.18% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 95% to the purification efficiency of NOx.
Embodiment 7: with the Mn (NO of 1.03g
3)
2Solution and 0.54gCo (NO
3)
26H
2O is mixed in polyvinylpyrrolidone (molecular weight the is 10000) aqueous solution of 50ml0.005mol/L, dropwise adds the ammoniacal liquor of 76ml0.1mol/L in the whipping process, continues to stir 1h, and ageing 2h makes nano level Co (OH)
2And Mn (OH)
2Colloidal sol; The 5g5A molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make modification 5A molecular sieve, wherein nano Co at 400 ℃ of following roasting 2h again
2O
3Content be 3%, nanometer MnO
2Content be 5%.
Take by weighing 4g modification 5A molecular sieve, 1.15g boehmite, 0.1g glycerine and be mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 18.54% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 89% to the purification efficiency of NOx.
Embodiment 8: with the Mn (NO of 1.03g
3)
2Solution and 0.45gCu (NO
3)
23H
2O is mixed in polyvinylpyrrolidone (molecular weight the is 10000) aqueous solution of 50ml0.005mol/L, dropwise adds the ammoniacal liquor of 95ml0.1mol/L in the whipping process, continues to stir 1h, and ageing 2h makes nano level Cu (OH)
2And Mn (OH)
2Colloidal sol; The 5g13X molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make modification 13X molecular sieve at 400 ℃ of following roasting 2h again, and wherein the content of nanometer CuO is 3%, nanometer MnO
2Content be 5%.
The 13X molecular sieve, 1.15g boehmite, the 0.1g glycerine that take by weighing after the 4g modification are mixed in the 8g deionized water, stir 0.5h, use HNO in the whipping process
3Regulating the slurry pH value is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 16.25% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 71% to the purification efficiency of NOx.
Embodiment 9: with the Mn (NO of 1.03g
3)
2Solution and 0.54gCo (NO
3)
26H
2O is mixed in polyvinylpyrrolidone (molecular weight the is 10000) aqueous solution of 50ml0.005mol/L, dropwise adds the ammoniacal liquor of 76ml0.1mol/L in the whipping process, continues to stir 1h, and ageing 2h makes nano level Co (OH)
2And Mn (OH)
2Colloidal sol; The 5g13X molecular sieve is sneaked in the colloidal sol, continue stirring and make its even dispersion; After stirring 1h, filter, 100 ℃ of dry 2h of the deposition that leaches promptly make modification 13X molecular sieve, wherein nano Co at 400 ℃ of following roasting 2h again
2O
3Content be 3%, nanometer MnO
2Content be 5%.
The 13X molecular sieve, 1.15g boehmite, the 0.1g glycerine that take by weighing the 4g modification are mixed in the 8g deionized water, stir 0.5h, and using HNO3 to regulate the slurry pH value in the whipping process is 3.5; Honeycomb ceramic carrier impregnated in 5min in the slurry, take out the back and purge with pressure-air and removes feed liquid unnecessary in the duct, place 120 ℃ of 550 ℃ of roasting 3h behind the dry 4h down, make scavenging material.It is 18.49% that this scavenging material active coating is uploaded rate.
The scavenging material that present embodiment makes is in Φ 16mm, the straight type glass tube of long 300mm reactor, NOx concentration is 4ppm, air speed 12000h
-1, under the normal temperature condition, be 85% to the purification efficiency of NOx.
Claims (5)
1. a monoblock type normal temperature trace nitrogen oxide scavenging material is characterized in that this scavenging material is is carrier with the cordierite honeycomb ceramic, through molecular sieve powder, the γ～Al of nano transition metal oxides modification
2O
3The composite material that composite material and additive are formed is an active coating, makes through roasting; Wherein the mass ratio of cordierite honeycomb ceramic and active coating is 10:1～20:7; The composition of described active coating and mass percent are:
Molecular sieve powder 20～80% after the nano transition metal oxides modification;
γ～Al
2O
3 18～78%；
Additive 2%;
The content of nano transition metal oxides is 1～8% of molecular sieve weight in the said modified molecular screen powder;
The concrete steps of the molecular sieve powder of described nano transition metal oxides modification are: transition metal nitrate is dissolved in the aqueous solution of polyvinylpyrrolidone that molecular weight is 10000 0.005mol/L; Dropwise add ammoniacal liquor in the stirring, be converted into the hydroxide of transition metal to transition metal nitrate fully; Continue to stir 1 hour, ageing 2～6 hours obtains the hydroxide sol of nano level transition metal; Molecular sieve is mixed in the colloidal sol to continue to stir makes its even dispersion; After filtration, washing, drying,, promptly get the molecular sieve of nano transition metal oxides modification 250～450 ℃ of roastings 2～4 hours.
2. monoblock type normal temperature trace nitrogen oxide scavenging material according to claim 1 is characterized in that described transition metal nitrate has: at least a nitrate in copper, manganese, cobalt, chromium, the iron.
3. monoblock type normal temperature trace nitrogen oxide scavenging material according to claim 1 is characterized in that described molecular sieve is 5A molecular sieve or 13X molecular sieve.
4. a method for preparing monoblock type normal temperature trace nitrogen oxide scavenging material according to claim 1 is characterized in that the concrete steps of this method are: with the molecular sieve powder after the modification and γ～Al
2O
3, additive is dissolved in the deionized water after the mixing and stirring, is prepared into slurry; Use HNO
3Regulating this slurry pH value is 2.5～4, makes coating paste, and slurry viscosity is 0.85～9.5mPas; Cordierite honeycomb ceramic carrier impregnated in the slurry 1～10 minute, take out the back and remove redundant sizing agent in the duct, dried 1～8 hour for 120 ℃; The oven dry back promptly makes this monoblock type normal temperature trace nitrogen oxide scavenging material 500～600 ℃ of roastings 2～6 hours, and it is 10～35% that active coating is uploaded rate.
5. method according to claim 4 is characterized in that described additive is at least a in ethylene glycol, isopropyl alcohol, glycerine and the polyethylene glycol.
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| CN103657632B (en) * | 2013-11-27 | 2015-08-26 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of base extraction monoblock type chromium oxide catalyst and preparation method and application |
| CN103990490B (en) * | 2014-05-16 | 2016-05-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Be used for monoblock type ozone catalytic agent of dyeing waste water and preparation method thereof |
| CN104984659A (en) * | 2015-06-24 | 2015-10-21 | 方耀 | Coal-fired flue gas denitrification method |
| CN105126822A (en) * | 2015-07-10 | 2015-12-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of monolithic low-concentration nitrogen monoxide normal-temperature manganese oxide catalyst |
| CN107159230B (en) * | 2017-05-23 | 2019-12-06 | 武汉工程大学 | Catalyst for normal-temperature catalytic removal of low-concentration nitrogen oxides and preparation method thereof |
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| WO2008086662A1 (en) * | 2007-01-04 | 2008-07-24 | East China University Of Science & Technology | Close coupled catalyst for purification of exhaust gas and the preparation thereof |
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