CN107855002A - A kind of method and its device of honeycomb fashion low-temperature denitration - Google Patents

A kind of method and its device of honeycomb fashion low-temperature denitration Download PDF

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Publication number
CN107855002A
CN107855002A CN201711215701.7A CN201711215701A CN107855002A CN 107855002 A CN107855002 A CN 107855002A CN 201711215701 A CN201711215701 A CN 201711215701A CN 107855002 A CN107855002 A CN 107855002A
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gas
catalyst
fixed bed
bed reactors
temperature
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曹鹏
赵勇刚
张�诚
王成志
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Shihezi University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/90Injecting reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • B01D2251/206Ammonium compounds
    • B01D2251/2062Ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/206Rare earth metals
    • B01D2255/2065Cerium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/2073Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/209Other metals
    • B01D2255/2092Aluminium

Abstract

The present invention relates to a kind of method and its device of honeycomb fashion low-temperature denitration, this method is specifically included first, and oxygen, nitrogen, carbon dioxide, CO gas and nitric oxide gas are mixed according to certain ratio, and is preheated;Secondly, the mixed gas after preheating and ammonia are mixed according to certain ratio, mixed gas is subjected to catalytic denitration processing according to certain flow by the fixed bed reactors provided with cellular catalyst;Finally, gas after treatment is discharged after supercooling by exhaust fan.Due to being coated using above-mentioned technical proposal, the inventive method using infusion process, technique is simple, and energy consumption is low, has good application prospect.After supported catalyst, honeycomb cordierite specific surface area dramatically increases, and active component is evenly distributed in carrier surface.Handled by concussion, it is found that active component and carrier is combined closely.Meanwhile Mn CeO2/Al2O3Catalyst raw material is easy to get, nonhazardous effect, and manufacturing cycle is shorter.

Description

A kind of method and its device of honeycomb fashion low-temperature denitration
Technical field
The present invention relates to a kind of method and its device of honeycomb fashion low-temperature denitration.
Background technology
Existing laboratory simulation equipment for denitrifying flue gas is only limitted to use powder catalyst, and loadings are milligram level, and carrier gas For inert gas or nitrogen, steam is brought into by carrier gas, larger with power plant actual denitrating technique difference, and simulates effect with actually making With situation, there is any discrepancy, it is impossible to evaluates denitrating catalyst well, is unfavorable for denitrating catalyst industrialization.
The content of the invention
In order to solve the above problems, it is an object of the invention to provide a kind of technique is simple, energy consumption is low, has preferably stable Property.And it is passed through SO2、H2O behind efficiencies are stable 65%, have a kind of side of honeycomb fashion low-temperature denitration of preferable anti-poisoning capability Method and its device.
The technical scheme is that:A kind of method of honeycomb fashion low-temperature denitration, this method specifically include following steps:
A kind of method of honeycomb fashion low-temperature denitration, it is characterised in that this method specifically includes following steps:
First, oxygen, nitrogen, carbon dioxide, carbon monoxide and nitric oxide gas are mixed according to certain ratio, and Preheated;
Secondly, the mixed gas after preheating and ammonia are mixed according to certain ratio, by mixed gas according to one Fixed flow carries out catalytic denitration processing by the fixed bed reactors provided with cellular catalyst;
Finally, gas after treatment is discharged after supercooling by exhaust fan.
Further, the temperature of the preheating is 80-200 DEG C.
Further, the flow is 5-100m3/h。
Further, the cellular catalyst layer is by Mn-CeO2/Al2O3Catalyst powder is made, the percentage of each component For Mn:10%-30%, Ce:60%-85%, Al:5%-20%.
Further, it is described prepare honeycomb cordierite denitrating catalyst preparation technology be:Using deionized water as solvent, weigh A certain amount of aluminum soluble salt, soluble cerium salt and soluble manganese salt are dissolved in deionized water respectively, stir 1.8-2.2h;
Then 15%-45% ammoniacal liquor stirring is added dropwise in mixed liquor, until pH=8-10, continues to stir 1-3h, It is unchanged to pH with deionized water rinsing after still aging 10-15h;
Finally in moving air atmosphere, temperature dries 10-15h under the conditions of being 100-120 DEG C, is 400-600 in temperature DEG C calcining 1-5h, be cooled to room temperature, obtain Mn-CeO2/Al2O3Catalyst powder;
Polyvinyl alcohol (PVA), emulsifier op-10 are added in deionized water, 0.5-5h is stirred, obtains creamy paste Liquid, it is slowly added to Mn-CeO2/Al2O3Powder, stir 0.5-3h.Honeycomb cordierite catalyst carrier is finally immersed in catalyst In slurry, aperture blowing, calcining, described low-temperature denitration catalyst is obtained.
Another object of the present invention provides above-mentioned implementation method and uses a kind of honeycomb fashion low-temperature denitration device, the denitrification apparatus Including carrier gas source steel cylinder, gas mixing tank, gas heating dress, steam react device, fixed bed reactors, gas cooler and Exhaust fan;
Wherein, the carrier gas source steel cylinder entering by pressure-reducing valve, mass flowmenter and check valve and the gas mixing tank Gas port UNICOM, the gas outlet of the gas mixing tank are connected with one end of gas heating assembling device, the gas heating dress The other end of device is connected by pipeline with one end of the fixed bed reactors, the other end of the fixed bed reactors and institute State one end connection of gas cooler, the air inlet UNICOM of the other end of the gas cooler and the exhaust fan;It is described The both ends of fixed bed reactors are provided with gas sampling mouth;The steam device that reacts passes through pipeline and the gas heating dress dress Put the pipeline UNICOM with fixed bed reactors.
Further, the fixed bed reactors Inner is provided with honeycomb fashion cordierite-base catalyst, and its aperture is 1-5mm.
Further, the number of the fixed bed reactors is at least one.
Further, the gas heating dress includes housing, heat-insulation layer, U-shaped heating tube and heater,
Wherein, the both ends of the housing are respectively equipped with air inlet and gas outlet, and the inside of the housing is provided with heat-insulation layer, if Do the U-shaped heating tube and be provided with the enclosure interior, the heater is connected with some U-shaped heating tubes.
The beneficial effects of the invention are as follows:Due to being coated using above-mentioned technical proposal, the inventive method using infusion process, technique Simply, energy consumption is low, has good application prospect.After supported catalyst, honeycomb cordierite specific surface area dramatically increases, activearm Divide and be evenly distributed in carrier surface.Handled by concussion, it is found that active component and carrier is combined closely.Meanwhile Mn-CeO2/ Al2O3Catalyst raw material is easy to get, nonhazardous effect, and manufacturing cycle is shorter.The temperature in use of existing denitrating catalyst is 300- 400 DEG C, the low temperature SCR denitration catalyst prepared by the present invention, when temperature in use is 100 DEG C, you can ensure 80% denitration Efficiency, and it is passed through SO2、H2O behind efficiencies are stable 65%, with preferable anti-poisoning capability.Therefore this can be urged magnificent agent to use After desulfurization, dedusting, dust and toxic action of the sulfur dioxide to catalyst are avoided, extends the service life of catalyst, carries The high service life of catalyst.
Brief description of the drawings
Fig. 1 is a kind of structural representation of honeycomb fashion low-temperature denitration device of the present invention.
In figure:
Embodiment:
The present invention is specifically described below by examples of implementation, to allow those skilled in the art more preferable The understanding present invention, but protection scope of the present invention is not limited to following embodiments.
As shown in figure 1, a kind of honeycomb fashion low-temperature denitration device of the present invention, the denitrification apparatus include carrier gas source steel cylinder, gas Blending tank, gas heating dress, steam react device, fixed bed reactors, gas cooler and exhaust fan;
Wherein, the carrier gas source steel cylinder entering by pressure-reducing valve, mass flowmenter and check valve and the gas mixing tank Gas port UNICOM, the gas outlet of the gas mixing tank are connected with one end of gas heating assembling device, the gas heating dress The other end of device is connected by pipeline with one end of the fixed bed reactors, the other end of the fixed bed reactors and institute State one end connection of gas cooler, the air inlet UNICOM of the other end of the gas cooler and the exhaust fan;It is described The both ends of fixed bed reactors are provided with gas sampling mouth;The steam device that reacts passes through pipeline and the gas heating dress dress Put the pipeline UNICOM with fixed bed reactors.
Further, the fixed bed reactors Inner is provided with honeycomb fashion cordierite-base catalyst, and its aperture is 1-5mm.
Further, the number of the fixed bed reactors is at least one.
Further, the gas heating dress includes housing, heat-insulation layer, U-shaped heating tube and heater,
Wherein, the both ends of the housing are respectively equipped with air inlet and gas outlet, and the inside of the housing is provided with heat-insulation layer, if Do the U-shaped heating tube and be provided with the enclosure interior, the heater is connected with some U-shaped heating tubes.
The method that low-temperature denitration is carried out using said apparatus, this method specifically include following steps:
First, oxygen, nitrogen, carbon dioxide, carbon monoxide and nitric oxide gas are mixed according to certain ratio, and Preheated;
Secondly, the mixed gas after preheating and ammonia are mixed according to certain ratio, by mixed gas according to one Fixed flow carries out catalytic denitration processing by the fixed bed reactors provided with cellular catalyst;
Finally, gas after treatment is discharged after supercooling by exhaust fan.
Further, the temperature of the preheating is 80-200 DEG C.
Further, the flow is 5-100m3/h。
Further, the cellular catalyst layer is by Mn-CeO2/Al2O3Catalyst powder is made, the percentage of each component For Mn:10%-30%, Ce:60%-85%, Al:5%-20%.
Further, it is described prepare honeycomb cordierite denitrating catalyst preparation technology be:Using deionized water as solvent, weigh A certain amount of aluminum soluble salt, soluble cerium salt and soluble manganese salt are dissolved in deionized water respectively, stir 1.8-2.2h;
Then 15%-45% ammoniacal liquor stirring is added dropwise in mixed liquor, until pH=8-10, continues to stir 1-3h, It is unchanged to pH with deionized water rinsing after still aging 10-15h;
Finally in moving air atmosphere, temperature dries 10-15h under the conditions of being 100-120 DEG C, is 400-600 in temperature DEG C calcining 1-5h, be cooled to room temperature, obtain Mn-CeO2/Al2O3Catalyst powder;
Polyvinyl alcohol (PVA), emulsifier op-10 are added in deionized water, 0.5-5h is stirred, obtains creamy paste Liquid, it is slowly added to Mn-CeO2/Al2O3Powder, stir 0.5-3h.Honeycomb cordierite catalyst carrier is finally immersed in catalyst In slurry, aperture blowing, calcining, described low-temperature denitration catalyst is obtained.
Embodiment 1
Catalyst activity evaluation catalyst usage amount is 4 pieces of 100mm × 100mm × 150mm honeycomb cordierite base catalyst, Reacted in fixed bed reactors, flow is controlled by mass flowmenter, and reaction condition is [NH3]/[NO]=1, NO amount is 200ppm, NH3=200ppm, flow 10m3/h.Tested according to temperature below gradient, specific data are as follows:
Temperature DEG C 90 100 110 120
Denitration efficiency 73.6% 83% 87.6% 92.9%
Embodiment 2
Catalyst activity evaluation catalyst usage amount is 4 pieces of 100mm × 100mm × 150mm honeycomb cordierite base catalyst, Reacted in fixed bed reactors, flow is controlled by mass flowmenter, and reaction condition is [NH3]/[NO]=1, NO amount is 200ppm, NH3=200ppm.Under the conditions of 100 DEG C of temperature, change air speed by changing flue gas flow, flue gas flow changes such as It is as a result as follows with Gradient:
Embodiment 3
Catalyst activity evaluation catalyst usage amount is 4 pieces of 100mm × 100mm × 150mm honeycomb cordierite base catalyst, Reacted in fixed bed reactors, flow is controlled by mass flowmenter, and reaction condition is 100 DEG C of temperature, and NO amount is 200ppm, flow 10m3/ h,.Change [NH3]/[NO] ratio, NO removal efficiencies are determined by flue gas analyzer.Between under the conditions of each Every 5 data of survey.As a result it is as follows:
[NH3]/[NO] 0.9 1.0 1.1
Denitration efficiency 71.5% 83% 78.6%
Embodiment 4
Catalyst activity evaluation catalyst usage amount is 4 pieces of 100mm × 100mm × 150mm honeycomb cordierite base catalyst, Reacted in fixed bed reactors, flow is controlled by mass flowmenter, and reaction condition is 100 DEG C of temperature, [NH3]/[NO]= 1, flow 10m3/h.Change NO concentration, it is as a result as follows:
NO concentration 100ppm 150ppm 200ppm 300ppm
Denitration efficiency 78.4% 79.1% 81.3% 79.6%
Embodiment 5
Catalyst activity evaluation catalyst usage amount is 4 pieces of 100mm × 100mm × 150mm honeycomb cordierite base catalyst, Aperture is respectively 1mm, 1.5mm, 2mm, 5mm, is reacted in fixed bed reactors, and flow is controlled by mass flowmenter, reaction Condition is 100 DEG C of temperature, and NO amount is 200ppm, NH3=200ppm, [NH3]/[NO]=1, flow 10m3/h.Change honeycomb Cordierite aperture, it is as a result as follows:

Claims (10)

  1. A kind of 1. method of honeycomb fashion low-temperature denitration, it is characterised in that this method specifically includes following steps:
    First, oxygen, nitrogen, carbon dioxide, carbon monoxide and nitric oxide gas are mixed according to certain ratio, and carried out Preheating;
    Secondly, the mixed gas after preheating and ammonia are mixed according to certain ratio, by mixed gas according to certain Flow carries out catalytic denitration processing by the fixed bed reactors provided with cellular catalyst;
    Finally, gas after treatment is discharged after supercooling by exhaust fan.
  2. 2. according to the method for claim 1, it is characterised in that the temperature of the preheating is 80-200 DEG C.
  3. 3. according to the method for claim 1, it is characterised in that the flow is 5-100m3/h。
  4. 4. according to the method for claim 1, it is characterised in that the cellular catalyst layer is by Mn-CeO2/Al2O3Catalysis Agent powder is made, and the percentage of each component is Mn:10%-30%, Ce:60%-85%, Al:5%-20%.
  5. 5. according to the method for claim 4, it is characterised in that the preparation work for preparing honeycomb cordierite denitrating catalyst Skill is:Using deionized water as solvent, weigh a certain amount of aluminum soluble salt, soluble cerium salt and soluble manganese salt and be dissolved in respectively In deionized water, 1.8-2.2h is stirred;
    Then 15%-45% ammoniacal liquor stirring is added dropwise in mixed liquor, until pH=8-10, continues to stir 1-3h, stands It is unchanged to pH with deionized water rinsing after ageing 10-15h;
    Finally in moving air atmosphere, temperature dries 10-15h under the conditions of being 100-120 DEG C, and being 400-600 DEG C in temperature forges 1-5h is burnt, room temperature is cooled to, obtains Mn-CeO2/Al2O3Catalyst powder;
    Polyvinyl alcohol (PVA), emulsifier op-10 are added in deionized water, 0.5-5h is stirred, obtains milky slurries, is delayed It is slow to add Mn-CeO2/Al2O3Powder, stir 0.5-3h.Honeycomb cordierite catalyst carrier is finally immersed in catalyst slurry In, aperture blowing, calcining, obtain described low-temperature denitration catalyst.
  6. A kind of 6. honeycomb fashion low-temperature denitration device, it is characterised in that the denitrification apparatus include carrier gas source steel cylinder, gas mixing tank, Gas heating dress, steam react device, fixed bed reactors, gas cooler and exhaust fan;
    Wherein, the carrier gas source steel cylinder passes through pressure-reducing valve, mass flowmenter and check valve and the air inlet of the gas mixing tank UNICOM, the gas outlet of the gas mixing tank are connected with one end of gas heating assembling device, and the gas heats assembling device The other end be connected by pipeline with one end of the fixed bed reactors, the other end of the fixed bed reactors and the gas One end connection of body cooler, the air inlet UNICOM of the other end of the gas cooler and the exhaust fan;The fixation The both ends of bed reactor are provided with gas sampling mouth;The steam react device by pipeline and the gas heat assembling device and The pipeline UNICOM of fixed bed reactors.
  7. 7. device according to claim 6, it is characterised in that the fixed bed reactors Inner is provided with honeycomb fashion cordierite-base Catalyst block, its aperture are 1-5mm.
  8. 8. device according to claim 6, it is characterised in that the number of the fixed bed reactors is at least one.
  9. 9. device according to claim 6, it is characterised in that gas heating dress includes housing, heat-insulation layer, U-shaped added Heat pipe and heater,
    Wherein, the both ends of the housing are respectively equipped with air inlet and gas outlet, and the inside of the housing is provided with heat-insulation layer, Ruo Gansuo State U-shaped heating tube and be provided with the enclosure interior, the heater is connected with some U-shaped heating tubes.
  10. 10. device according to claim 6, it is characterised in that the carrier gas source steel cylinder includes oxygen bottle, nitrogen steel Bottle, carbon dioxide steel cylinder, carbon monoxide steel cylinder and nitric oxide steel cylinder, the oxygen bottle, nitrogen cylinder, titanium dioxide carbon steel Battery valve, pressure-reducing valve and flowmeter are provided with the bottleneck of bottle, carbon monoxide steel cylinder and nitric oxide steel cylinder.
CN201711215701.7A 2017-11-28 2017-11-28 A kind of method and its device of honeycomb fashion low-temperature denitration Pending CN107855002A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108426975A (en) * 2018-05-15 2018-08-21 东莞诺维新材料科技有限公司 A kind of catalyst activity evaluating apparatus
CN110721673A (en) * 2019-09-12 2020-01-24 华中科技大学 Mn-Ce/Al2O3Cordierite low-temperature denitration catalyst and preparation method thereof
CN112191098A (en) * 2020-09-30 2021-01-08 江苏扬子催化剂有限公司 Low-temperature denitration granular catalyst and honeycomb catalyst series-parallel combined reaction process

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CN102553574A (en) * 2012-01-17 2012-07-11 山东大学 Method for preparing flue gas SCR (Selective Catalytic Reduction) denitration catalyst
CN103433040A (en) * 2013-08-29 2013-12-11 天津大学 Binary metal modified titanium dioxide catalyst, preparation method thereof and application of catalyst in removal of nitric oxide contained in tail gas of diesel engine
CN103529161A (en) * 2013-08-19 2014-01-22 广东电网公司电力科学研究院 Detection device and method for activity of catalyst of selective catalytic reduction method denitration system
CN203479784U (en) * 2013-09-06 2014-03-12 广东电网公司电力科学研究院 Catalyst activity detection experimental device of SCR (selective catalytic reduction) denitration system
CN105854874A (en) * 2016-05-12 2016-08-17 石河子大学 Denitrification catalyst, preparation method of denitrification catalyst and application of denitrification catalyst in flue gas denitrification
CN106732758A (en) * 2015-11-19 2017-05-31 中国石油化工股份有限公司 A kind of low-temperature denitration catalyst and preparation method thereof
CN207822801U (en) * 2017-11-28 2018-09-07 石河子大学 A kind of device of honeycomb fashion low-temperature denitration

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102553574A (en) * 2012-01-17 2012-07-11 山东大学 Method for preparing flue gas SCR (Selective Catalytic Reduction) denitration catalyst
CN103529161A (en) * 2013-08-19 2014-01-22 广东电网公司电力科学研究院 Detection device and method for activity of catalyst of selective catalytic reduction method denitration system
CN103433040A (en) * 2013-08-29 2013-12-11 天津大学 Binary metal modified titanium dioxide catalyst, preparation method thereof and application of catalyst in removal of nitric oxide contained in tail gas of diesel engine
CN203479784U (en) * 2013-09-06 2014-03-12 广东电网公司电力科学研究院 Catalyst activity detection experimental device of SCR (selective catalytic reduction) denitration system
CN106732758A (en) * 2015-11-19 2017-05-31 中国石油化工股份有限公司 A kind of low-temperature denitration catalyst and preparation method thereof
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CN207822801U (en) * 2017-11-28 2018-09-07 石河子大学 A kind of device of honeycomb fashion low-temperature denitration

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108426975A (en) * 2018-05-15 2018-08-21 东莞诺维新材料科技有限公司 A kind of catalyst activity evaluating apparatus
CN108426975B (en) * 2018-05-15 2023-12-26 东莞诺维新材料科技有限公司 Catalyst activity evaluation device
CN110721673A (en) * 2019-09-12 2020-01-24 华中科技大学 Mn-Ce/Al2O3Cordierite low-temperature denitration catalyst and preparation method thereof
CN112191098A (en) * 2020-09-30 2021-01-08 江苏扬子催化剂有限公司 Low-temperature denitration granular catalyst and honeycomb catalyst series-parallel combined reaction process

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Application publication date: 20180330