CN108435153A - Stephanoporate thin wall SCR honeycomb catalyst special carriers and its preparation method and application - Google Patents
Stephanoporate thin wall SCR honeycomb catalyst special carriers and its preparation method and application Download PDFInfo
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- CN108435153A CN108435153A CN201810167243.2A CN201810167243A CN108435153A CN 108435153 A CN108435153 A CN 108435153A CN 201810167243 A CN201810167243 A CN 201810167243A CN 108435153 A CN108435153 A CN 108435153A
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- honeycomb catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000000969 carrier Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 25
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- ZYPJORZNHDXKSD-UHFFFAOYSA-N oxotitanium;sulfuric acid Chemical compound [Ti]=O.OS(O)(=O)=O ZYPJORZNHDXKSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KZRXPHCVIMWWDS-AWEZNQCLSA-N (4S)-4-amino-5-dodecanoyloxy-5-oxopentanoic acid Chemical compound CCCCCCCCCCCC(=O)OC(=O)[C@@H](N)CCC(O)=O KZRXPHCVIMWWDS-AWEZNQCLSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229940071085 lauroyl glutamate Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses stephanoporate thin wall SCR honeycomb catalyst special carriers and its preparation method and application, it includes the following steps:(1), pass through high-concentration sulfuric acid oxygen titanium solution, plus seed minute-pressure method hydrolysis, be made small particle hydrolyze metatitanic acid;(2), hydrolysis be made metatitanic acid;(3), by step(1)With(2)Metatitanic acid mixing, wash twice;(4), catalytic treatment when add it is surfactant-modified, increase its calcining after surface mobility;(5), addition ammonium hydroxide adjust pH to 9.0 ~ 9.2, insulated and stirred 2h;(6), addition antioxidant and reinforcing agent;(7), calcined by rotary kiln 8h obtain pie material;(8), obtain powder after pie crushing material.The beneficial effects of the invention are as follows suitable for porous(It is more than 50 holes)Thin-walled(Wall thickness is less than 0.5mm)Honeycomb catalyst, solve the raw materials for production demand of stephanoporate thin wall catalyst.
Description
Technical field
The present invention relates to the outer of the periphery for covering the cellular construction body with honeycomb cell structure body and setting
Honeycomb catalyst carrier more particularly to SCR honeycomb catalyst special carriers of wall and its preparation method and application.
Background technology
It is used as loading nitrogen oxides (NOx), carbon monoxide (CO), hydrocarbon in purifying motor discharge gas
(HC) catalyst carrier of catalyst such as.Honeycomb catalyst carrier is made of the porous material with multiple holes, and forms tool
There is the honeycomb in the hole as fluid flowing path.(each aperture can be separated by the way that catalyst solution to be injected into inside unit
Partition wall), then dry and baking, to supported catalyst.Problem is had become to the control of discharge gas in recent years, for taking
There are many demand for being downloaded to the large, honeycomb catalyst of the truck conspicuity marking such as truck, bus.
Chinese invention patent publication number CN1684770 discloses honeycomb catalyst carrier and its manufacturing method, has single
Meta structure body (1), which, which becomes, is made of the porous material with multiple apertures and with the bee of multiple units
Nest shape;And the outer wall (6) for the periphery with capping unit structure (1) being made of porous material.In cellular construction body (1)
In porous material there is certain thickness outermost circumferential portion to be formed with impregnation section, which is saturated with can be by burning
The water-insoluble organic material or inorganic material to disappear.But the carrier sulfur content is high, and poor water retention property is not suitable for catalyst prod
It is quickly kneaded, is not also suitable for porous(It is more than 50 holes)Thin-walled(Wall thickness is less than 0.5mm)Honeycomb catalyst.
Invention content
The technical problem to be solved by the present invention is to existing honeycomb catalyst carrier sulfur content height, poor water retention property is not suitable for
It is quickly kneaded in catalyst prod, is not also suitable for the honeycomb catalyst of stephanoporate thin wall, a kind of stephanoporate thin wall SCR bees are provided thus
Nest catalyst special carrier and its preparation method and application.
The technical scheme is that:The preparation method of stephanoporate thin wall SCR honeycomb catalyst special carriers, it includes following
Step:(1), pass through high-concentration sulfuric acid oxygen titanium solution, plus seed minute-pressure method hydrolysis, be made small particle hydrolyze metatitanic acid, grain size
Control D50 < 1.8um, D90 < 2.2um, component 80 ~ 95%;(2), hydrolysis be made metatitanic acid, size controlling D50 < 2.0um,
D90 < 2.7um, component 5% ~ 20%;(3), by step(1)With(2)Metatitanic acid mixing control Fe contents by washing twice
< 60ppm, Ka content < 60ppm, Na content < 60ppm;(4), catalytic treatment when add surfactant-modified, increase it and forge
Surface mobility after burning is warming up to 50 ~ 55 DEG C, insulated and stirred 3h;(5), addition ammonium hydroxide adjust pH to 9.0 ~ 9.2, heat preservation is stirred
Mix 2h;(6), addition antioxidant and reinforcing agent;(7), calcined by rotary kiln 8h obtain pie material, high temperature section control temperature 580 ~
620℃;(8), obtain the powder of grain size 1.0um < D50 < 1.2um, 5um < D90 < 12um after pie crushing material;(9), powder
End control water absorption makes its dispersibility≤25um, SO3 contents control below 1.5% in 68 ~ 72g/100g, the stirring of alcohol acid system.
Step in said program(4)In surfactant be lauroyl glutamate, additive amount is total TiO2's
0.03~0.05%。
Step described in said program(6)In antioxidant be ammonium paratungstate, wherein 4.5% < WO3 < 5.0%, enhancing
Agent is the superfine silicon dioxide of 0.8% < SiO2 < 1.3%.
Stephanoporate thin wall SCR honeycomb catalyst special carriers, it is by the above-mentioned special load of stephanoporate thin wall SCR honeycomb catalysts
The preparation method of body is made.
The application of stephanoporate thin wall SCR honeycomb catalyst special carriers, it is used for stephanoporate thin wall SCR honeycomb catalysts.
The beneficial effects of the invention are as follows suitable for porous(It is more than 50 holes)Thin-walled(Wall thickness is less than 0.5mm)Honeycomb catalysis
Agent, sulfur content is low, good water-retaining property, is quickly kneaded suitable for catalyst prod, the low operating mode of honeycomb catalyst product extrusion pressure,
Solves the raw materials for production demand of stephanoporate thin wall catalyst.
Specific implementation mode
With reference to embodiment, the present invention will be further described.
Embodiment 1:The preparation method of stephanoporate thin wall SCR honeycomb catalyst special carriers, it includes the following steps:(1), it is logical
Excessive concentrations titanyl sulfate solution, the hydrolysis of plus seed minute-pressure method are made small particle and hydrolyze metatitanic acid, size controlling D50 <
1.8um, D90 < 2.2um, component 80%;(2), hydrolysis be made metatitanic acid, size controlling D50 < 2.0um, D90 < 2.7um,
Component 5%;(3), by step(1)With(2)Metatitanic acid mixing, by washing twice, control Fe content < 60ppm, Ka contents <
60ppm, Na content < 60ppm;(4), catalytic treatment when addition surfactant lauroyl glutamate be modified, additive amount is
The 0.03% of total TiO2 increases the surface mobility after its calcining, is warming up to 50 DEG C, insulated and stirred 3h;(5), addition ammonium hydroxide adjust
PH to 9.0, insulated and stirred 2h;(6), addition antioxidant ammonium paratungstate and reinforcing agent superfine silicon dioxide, in ammonium paratungstate
4.5% < WO3 < 5.0%, 0.8% < SiO2 < 1.3% in superfine silicon dioxide;(7), calcined by rotary kiln 8h obtain pie material,
Control 580 DEG C of temperature;(8), obtain the powder of grain size 1.0um < D50 < 1.2um, 5um < D90 < 12um after pie crushing material
End;(9), powder control water absorption in 68g/100g, the stirring of alcohol acid system makes its dispersibility≤25um, the control of SO3 contents exist
1.5% or less.
Embodiment 2:The preparation method of stephanoporate thin wall SCR honeycomb catalyst special carriers, it includes the following steps:(1), it is logical
Excessive concentrations titanyl sulfate solution, the hydrolysis of plus seed minute-pressure method are made small particle and hydrolyze metatitanic acid, size controlling D50 <
1.8um, D90 < 2.2um, component 88%;(2), hydrolysis be made metatitanic acid, size controlling D50 < 2.0um, D90 < 2.7um,
Component 12%;(3), by step(1)With(2)Metatitanic acid mixing control Fe content < 60ppm, Ka contents by washing twice
< 60ppm, Na content < 60ppm;(4), catalytic treatment when addition surfactant lauroyl glutamate be modified, additive amount
It is the 0.04% of total TiO2, increases the surface mobility after its calcining, be warming up to 52 DEG C, insulated and stirred 3h;(5), addition ammonium hydroxide tune
Save pH to 9.1, insulated and stirred 2h;(6), addition antioxidant ammonium paratungstate and reinforcing agent superfine silicon dioxide, in ammonium paratungstate
4.5% < WO3 < 5.0%, 0.8% < SiO2 < 1.3% in superfine silicon dioxide;(7), calcined by rotary kiln 8h obtain pie material,
Control 600 DEG C of temperature;(8), obtain the powder of grain size 1.0um < D50 < 1.2um, 5um < D90 < 12um after pie crushing material
End;(9), powder control water absorption in 70g/100g, the stirring of alcohol acid system makes its dispersibility≤25um, the control of SO3 contents exist
1.5% or less.
Embodiment 3:The preparation method of stephanoporate thin wall SCR honeycomb catalyst special carriers, it includes the following steps:(1), it is logical
Excessive concentrations titanyl sulfate solution, the hydrolysis of plus seed minute-pressure method are made small particle and hydrolyze metatitanic acid, size controlling D50 <
1.8um, D90 < 2.2um, component 95%;(2), hydrolysis be made metatitanic acid, size controlling D50 < 2.0um, D90 < 2.7um,
Component 20%;(3), by step(1)With(2)Metatitanic acid mixing control Fe content < 60ppm, Ka contents by washing twice
< 60ppm, Na content < 60ppm;(4), catalytic treatment when addition surfactant lauroyl glutamate be modified, additive amount
It is the 0.05% of total TiO2, increases the surface mobility after its calcining, be warming up to 55 DEG C, insulated and stirred 3h;(5), addition ammonium hydroxide tune
Save pH to 9.2, insulated and stirred 2h;(6), addition antioxidant ammonium paratungstate and reinforcing agent superfine silicon dioxide, in ammonium paratungstate
4.5% < WO3 < 5.0%, 0.8% < SiO2 < 1.3% in superfine silicon dioxide;(7), calcined by rotary kiln 8h obtain pie material,
Control 620 DEG C of temperature;(8), obtain the powder of grain size 1.0um < D50 < 1.2um, 5um < D90 < 12um after pie crushing material
End;(9), powder control water absorption in 72g/100g, the stirring of alcohol acid system makes its dispersibility≤25um, the control of SO3 contents exist
1.5% or less.
Step(1)With(2)By producing two kinds of metatitanic acids respectively, the distribution of guarantee washing metatitanic acid grain size is easy to wash,
And also to meet the particle diameter distribution of finished product;Step(3)In by washing twice, secondary washing time be not less than 5h, one washes
Not less than 4h, it is ensured that iron, potassium, sodium content meet Fe content < 60ppm, Ka content < 60ppm, Na content < 60ppm.
Present invention is particularly suitable for the raw materials for doing stephanoporate thin wall SCR honeycomb catalysts.
Claims (5)
1. the preparation method of stephanoporate thin wall SCR honeycomb catalyst special carriers, it is characterized in that it includes the following steps:(1), pass through
High-concentration sulfuric acid oxygen titanium solution, the hydrolysis of plus seed minute-pressure method are made small particle and hydrolyze metatitanic acid, size controlling D50 <
1.8um, D90 < 2.2um, component 80 ~ 95%;(2), hydrolysis be made metatitanic acid, size controlling D50 < 2.0um, D90 <
2.7um, component 5% ~ 20%;(3), by step(1)With(2)Metatitanic acid mixing, by washing twice, control Fe contents <
60ppm, Ka content < 60ppm, Na content < 60ppm;(4), catalytic treatment when add surfactant-modified, increase its calcining
Surface mobility afterwards is warming up to 50 ~ 55 DEG C, insulated and stirred 3h;(5), addition ammonium hydroxide adjust pH to 9.0 ~ 9.2, insulated and stirred
2h;(6), addition antioxidant and reinforcing agent;(7), calcined by rotary kiln 8h obtain pie material, control 580 ~ 620 DEG C of temperature;
(8), obtain the powder of grain size 1.0um < D50 < 1.2um, 5um < D90 < 12um after pie crushing material;(9), powder control
Water absorption makes its dispersibility≤25um, SO3 contents control below 1.5% in 68 ~ 72g/100g, the stirring of alcohol acid system.
2. the preparation method of stephanoporate thin wall SCR honeycomb catalyst special carriers as described in claim 1, it is characterized in that the step
Suddenly(4)In surfactant be lauroyl glutamate, additive amount is the 0.03 ~ 0.05% of total TiO2.
3. the preparation method of stephanoporate thin wall SCR honeycomb catalyst special carriers as described in claim 1, it is characterized in that the step
Suddenly(6)In antioxidant be ammonium paratungstate, wherein 4.5% < WO3 < 5.0%, reinforcing agent is the super of 0.8% < SiO2 < 1.3%
Fine silica.
4. stephanoporate thin wall SCR honeycomb catalyst special carriers, it is characterized in that using any stephanoporate thin walls of claim 1-3
The preparation method of SCR honeycomb catalyst special carriers is made.
5. the application of stephanoporate thin wall SCR honeycomb catalyst special carriers as described in any one of claims 1-3, it is characterized in that it is used
In stephanoporate thin wall SCR honeycomb catalysts.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4113660A (en) * | 1975-12-23 | 1978-09-12 | Sakai Chemical Industry Co., Ltd. | Production of shaped catalysts or carriers comprising titanium oxides |
CN101318697A (en) * | 2008-07-11 | 2008-12-10 | 四川华铁钒钛科技股份有限公司 | Method for preparing titanium dioxide product for high-specific surface area denitrating catalyst |
CN106944039A (en) * | 2017-02-21 | 2017-07-14 | 安徽迪诺环保新材料科技有限公司 | The production method of 40 hole above honeycomb denitration catalyst carrier materials |
-
2018
- 2018-02-28 CN CN201810167243.2A patent/CN108435153A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4113660A (en) * | 1975-12-23 | 1978-09-12 | Sakai Chemical Industry Co., Ltd. | Production of shaped catalysts or carriers comprising titanium oxides |
CN101318697A (en) * | 2008-07-11 | 2008-12-10 | 四川华铁钒钛科技股份有限公司 | Method for preparing titanium dioxide product for high-specific surface area denitrating catalyst |
CN106944039A (en) * | 2017-02-21 | 2017-07-14 | 安徽迪诺环保新材料科技有限公司 | The production method of 40 hole above honeycomb denitration catalyst carrier materials |
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