CN109589969A - Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Eu-Ce composite catalyst - Google Patents
Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Eu-Ce composite catalyst Download PDFInfo
- Publication number
- CN109589969A CN109589969A CN201811576278.8A CN201811576278A CN109589969A CN 109589969 A CN109589969 A CN 109589969A CN 201811576278 A CN201811576278 A CN 201811576278A CN 109589969 A CN109589969 A CN 109589969A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- total
- aluminium manganese
- pillared montmorillonite
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 75
- -1 Aluminium manganese Chemical compound 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims abstract description 4
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 230000020477 pH reduction Effects 0.000 claims description 10
- 239000004575 stone Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 229910021647 smectite Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007689 inspection Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims 3
- 239000011261 inert gas Substances 0.000 claims 2
- 239000011148 porous material Substances 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 claims 1
- 239000011435 rock Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 107
- 230000003197 catalytic effect Effects 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 11
- 235000019391 nitrogen oxide Nutrition 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002089 NOx Inorganic materials 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(III) nitrate Inorganic materials [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides the preparation method and application that aluminium manganese is total to pillared montmorillonite load Eu-Ce composite catalyst.The preparation that aluminium manganese is total to pillared montmorillonite carrier is that acidifying montmorillonite and hydroxy Al manganese solution are mixed, and hydroxy Al manganese solution is made to enter acidifying montmorillonite between layers, then the aluminium manganese as made from calcining is total to pillared montmorillonite carrier；Then pillared montmorillonite carrier is total to by praseodymium nitrate and cerous nitrate solution mixed solution and aluminium manganese and 1~4 hour, rotary evaporation drying is mixed, roasted and composite catalyst is made.There is catalyst of the present invention biggish specific surface area, orderly aluminium manganese delaminated structure and Eu and Ce to load；The catalyst removes denitrification for low-temperature catalyzed reduction, has high efficiency and stability.And the catalyst (100 DEG C~300 DEG C) under lower temperature range keeps NO initial conversion in 100 hours.Catalyst preparation materials of the present invention are cheap and preparation process is simple.
Description
Technical field
The present invention relates to the systems that a kind of aluminium manganese for catalytic removal NO is total to pillared montmorillonite load Eu-Ce composite catalyst
Preparation Method and its under cryogenic selective catalysis eliminate the application of NO.
Background technique
While Chinese society economy is grown rapidly, also along with the continuous growth of energy consumption, corresponding coal and petroleum combustion
The discharge for the industrial waste gas that material burning generates constitutes serious threat to the environment in China, wherein the most important atmosphere discharged
One of pollutant is exactly nitrogen oxides (NOx).Usually said nitrogen oxides (nitrogenoxides) includes six kinds of valence states
Compound, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), nitrogen trioxide (N2O3), four oxidation two
Nitrogen (N2O4) and dinitrogen pentoxide (N2O5) etc., it is NO that wherein ratio is maximum.Nitrogen oxides (NOx) is in addition to meeting is to human health
Serious environmental problem can be also generated outside having a direct impact, such as with NO and NO2Based on nitrogen oxides be to be formed acid rain and
One important element of chemical fumes.Discharge of pollutant sources, which is irradiated to NO_x in Air Environment and hydrocarbon through ultraviolet light, to be occurred
The toxic smog that photochemical reaction is formed, referred to as photochemical fog reduce atmospheric visibility.Nitrogen oxides meets water steaming in air
Gas will form acidic materials, drop to ground and then forms acid rain.Acid rain has corrosivity, since coverage extensively can be to the mankind
Existence and production and the existence of crops and other animals and plants cause tremendous influence.In addition, the NOx drifted in an atmosphere can also
With the O in stratosphere3It reacts, to break O3Balance, leads to O3The consume of layer, to the mankind, animals and plants or even the entire earth
Cause catastrophic collapse.Therefore, the emission problem of nitrogen oxides, which has appeared vividly to become, influences today's society harmony, restricts economic hair
One of an important factor for exhibition, destruction human survival, control and improvement nitrogen oxides (nitrogen oxides) are current research
Hot spot.Due to administering NOxDifficulty is big, control and improvement NOxPollution has become one of most active project in current environmental protection research.
There are many eliminate NO both at home and abroad at presentxMethod, wherein NH3Selective Catalytic Reduction of NOxMethod comparative maturity, applied
In vehicle exhaust (stationary source) and thermal power plant (moving source) NOxThe improvement of pollution.NH3Your gold-SCR catalysis material mainly has
4 kinds of metal catalyst, metal oxide catalyst, molecular sieve catalyst and other catalysis materials systems, wherein V2O5-WO3
(MoO3)/TiO2System is most widely used, and the system has been commercialized at present, but V2O5-WO3(MoO3)/TiO2Catalyst system
There are low temperature active deficiencies and high temperature V (vanadium) volatilization to generate secondary pollution problems.
In recent years, have that economic cost is low, less energy consumption, carrying capacity of environment in terms of denitrating flue gas due to column clay (PILC)
Low, the features such as being not likely to produce secondary pollution, has been increasingly becoming the hot spot of society research.In addition, column clay (PILC) has
NH3The required primary condition of-SCR reaction: column clay shows good thermal stability, avoids what catalyst easily occurred
Sintering Problem；Biggish specific surface area and suitable aperture structure are conducive to the absorption and reaction of reactant；A large amount of acid is provided
Property site, is easy to NH3And NO absorption and form active material, thus promote catalysis react.Just because of this column clay
(PILC) catalytic performance is excellent, is widely used to the catalytic fields such as coal chemical industry, PETROLEUM PROCESSING and fine chemistry industry at present.This patent
It is carrier that aluminium manganese, which is total to pillared montmorillonite, is prepared into Al-Mn-PILC by rotary evaporation and loads the compound catalysis of Eu and Ce
Agent obtains catalytic removal NO high activity and high stability energy in good temperature range (100 DEG C~300 DEG C).Just at present
It is most of to use independent pillared side although other pillared montmorillonites also have preferable activity from the point of view of the document being had been reported that
Simultaneously supported rare earth element prepares catalyst to method, and reaction temperature is relatively narrow, and activity is poor, and Eu-Ce/Al-Mn- prepared by this patent
PILC catalyst has preferable activity under cryogenic.The implementation of this project obtains: project of national nature science fund project (is compiled
Number: 21277008；20777005)；Beijing Natural Science Fund In The Light (number: 8082008)；State key research and development plan
(No.2017YFC0209905) research contents of subsidy and these projects.
Summary of the invention
The object of the present invention is to provide a kind of aluminium manganese be total to pillared montmorillonite load Eu and Ce composite catalyst preparation and
It is used for catalytic removal NO pollutant.The BET specific surface area volume of montmorillonite is 48m2The pillared illiteracy of aluminium manganese of/g, Eu and Ce load
For the BET specific surface area of de- stone compared with montmorillonite original soil, increase is very big, is 150m2/g.Provided catalyst can be lower
Under reaction temperature (100 DEG C~300 DEG C), efficiently NO (30%~94% NO conversion ratio) is eliminated.Moreover, this catalyst have compared with
High stability.This catalyst preparation process is simple, and raw material are widely present in nature.
The present invention provides a kind of aluminium manganese for catalytic removal NO and is total to pillared montmorillonite load Eu and Ce composite catalyst
Preparation method:
(1) by the H of natural smectite and 1.2~1.8mol/L2SO4Solution stirring in water bath 4~6 hours at 60-70 DEG C,
Wherein montmorillonite and H2SO4The ratio of solution is 1g:10ml, the montmorillonite filtration washing after acidification to no SO4 2-Until (use
BaCl2Solution is examined), filtered sample 120 DEG C of dry 6h in drying box, ground 80 mesh sieve of mistake of sample after drying
It is modified montmorillonite used up to acid.By the AlCl of 0.1~0.3mol/L3Aqueous solution and 0.1~0.2mol/L MnCl2Aqueous solution is with [Al3 +]/[Mn2+] molar ratio=1:0~0.6 mixing, the NaOH solution of 0.1~0.3mol/L is slowly dripped with the speed of 1mL/min
It is added in above-mentioned solution, [OH-]/[Al3++Mn2+] (molar ratio)=2~3, temperature keep 60~70 DEG C, be subsequently agitated for 3~6
Hour, resulting suspension aged at room temperature 12~24 hours obtains aluminium manganese column liquid.By above-mentioned acidified modified montmorillonite according to certain
Ratio be added deionized water in acidifying montmorillonite suspension slurry is made, acidifying montmorillonite: deionized water (mass ratio)=1:40
~80.The above aluminium manganese column liquid is added dropwise to dropwise in acidifying montmorillonite suspension slurry, wherein ([Al3+]+[Mn2+]): acidification is covered
De- stone=4~10mmol:1g, 60~70 DEG C of holding temperature stirring 10~16 hours, aged at room temperature 12~24 hours, 100~120
The sieving of DEG C drying and grinding, then puts it into Muffle furnace, rises to 300~450 DEG C with 1~2 DEG C/min heating rate, keep this
Temperature section is calcined 1~4 hour, and gained sample is aluminium manganese pillared montmorillonite.Aluminium manganese made above is total to pillared montmorillonite to be added
0.002mol/L~0.008mol/LEu (NO3)3With Ce (NO3)3In solution, 60~75 DEG C of 1~4h of stirring, wherein aluminium manganese is total to column
Support montmorillonite and Eu (NO3)3Ratio is 100g:0.006mol~0.018mol, and aluminium manganese is total to pillared montmorillonite and Ce (NO3)3Ratio
For 100g:0.003mol~0.007mol, rotary evaporated to dryness is dry, and 100~120 DEG C of dryings 12~for 24 hours, 400 DEG C of roastings 1~
Support type Eu-Ce/Al-Mn-PILC composite catalyst is made in 4h.
(2) catalyst of the present invention is normal pressure 1atm in reaction pressure, (10,000h under high-speed-1~100,000h-1)、O2
Concentration (5vl.%~10vl.%), high H2O content (1vl.%~10vl.%), NH3Concentration (330ppm~1100ppm), NO are dense
It spends (300ppm~1000ppm) and Balance Air is N2Under the conditions of, in wide temperature range (100 DEG C~300 DEG C), have high
Catalytic activity (NO conversion ratio=30%~95%)；It is normal pressure 1atm in reaction pressure, (10,000h under high-speed-1~200,
000h-1), high O2Concentration (5vl.%~10vl.%), H2O content (1vl.%~10vl.%), NH3Concentration (330ppm~
1100ppm), NO concentration (300ppm~1000ppm) and Balance Air are N2Under the conditions of, investigate the compound Eu-Ce/Al-Mn- of support type
PILC catalyst, in a temperature spot of lower temperature section (100 DEG C~300 DEG C), NO conversion ratio in 100 hours is being studied
Temperature range under, catalytic activity still maintains high stability, shows high stability.
Detailed description of the invention
Fig. 1 is Ce/Al-Mn-PILC, Eu/Al-Mn-PILC, Eu-Ce/Al- prepared by the embodiment of the present invention 1,2,3 and 4
The XRD diagram of Mn-PILC-I, Eu-Ce/Al-Mn-PILC-II catalyst.
Fig. 2 is Ce/Al-Mn-PILC, Eu/Al-Mn-PILC, Eu-Ce/Al- prepared by the embodiment of the present invention 1,2,3 and 4
The N of Mn-PILC-I, Eu-Ce/Al-Mn-PILC-II catalyst2Absorption/desorption figure.
Fig. 3 is Ce/Al-Mn-PILC, Eu/Al-Mn-PILC, Eu-Ce/Al- prepared by the embodiment of the present invention 1,2,3 and 4
NH on Mn-PILC-I, Eu-Ce/Al-Mn-PILC-II catalyst3Selective Catalytic Reduction of NO activity.
Fig. 4 is Ce/Al-Mn-PILC, Eu/Al-Mn-PILC, Eu-Ce/Al- prepared by the embodiment of the present invention 1,2,3 and 4
The stability of 250 DEG C of reactions 100 hours of Mn-PILC-I, Eu-Ce/Al-Mn-PILC-II catalyst.
Specific embodiment
Embodiment 1
(1) by the H of natural smectite and 1.2mol/L2SO4Solution stirring in water bath 4 hours at 60 DEG C, wherein montmorillonite with
H2SO4The ratio of solution is 1g:10ml, the montmorillonite filtration washing after acidification to no SO4 2-Until (use BaCl2Solution is examined),
Filtered sample 120 DEG C of dry 6h in drying box, ground 80 mesh sieve of mistake of sample after drying take off up to modified cover of acid
Stone.By the AlCl of 0.1mol/L3Aqueous solution and 0.1mol/LMnCl2Aqueous solution is with [Al3+]/[Mn2+] molar ratio=1:0.1 is mixed
It closes, by the NaOH solution of 0.1mol/L, keeps [OH-]/[Al3++Mn2+] (molar ratio)=2, it is slowly dripped with the speed of 1mL/min
It is added in above-mentioned solution, temperature is kept for 60 DEG C, is subsequently agitated for 3 hours, resulting suspension aged at room temperature 12 hours obtains aluminium manganese
Column liquid.Above-mentioned acidified modified montmorillonite is added according to a certain percentage in deionized water, acidifying montmorillonite suspension slurry is made
Liquid, acidifying montmorillonite: deionized water (mass ratio)=1:40.The above aluminium manganese column liquid is added dropwise to acidifying montmorillonite dropwise to suspend
In slurries, wherein ([Al3+]+[Mn2+]): acidifying montmorillonite=4mmol:1g keeps 60 DEG C of temperature to stir 12 hours, and room temperature is old
Change 12 hours, 100 DEG C of drying and grinding sievings then put it into Muffle furnace, rise to 300 DEG C with 2 DEG C/min heating rate, protect
Hold this temperature section calcining 1 hour, gained sample is Al-Mn-PILC.By Ce (NO3)3It is molten in deionized water, being made into concentration is
0.002mol/L solution loads aluminium manganese pillared montmorillonite mass ratio (Ce wt%=0.5wt%) by Ce, and it is above dense to calculate gained
The cerous nitrate solution volume of degree is added in the above-mentioned aluminium manganese pillared montmorillonite of 4g, is slurried presoma, 60 DEG C of stirring 1h, rotation
Be evaporated to drying, 100 DEG C drying 12 hours, 400 DEG C of roasting 1h, support type Ce/Al-Mn-PILC composite catalyst is made.
(2) catalyst of the present invention is normal pressure 1atm in reaction pressure, 10,000h under air speed-1、O2Concentration 5vl.%, height
H2O content 1vl.%, NH3Concentration is that 330ppm, NO concentration are 300ppm and N2Under the conditions of Balance Air, in lower temperature
In range (100 DEG C~300 DEG C), catalytic removal low concentration of NO with higher is active (NO conversion ratio=13%~82%)；?
Reaction pressure is normal pressure 1atm, 10,000h under air speed-1、O2Concentration 5vl.%, H2O content 1vl.%, NH3Concentration be 330ppm,
NO concentration is 300ppm and N2Under the conditions of Balance Air, investigation Ce/Al-Mn-PILC catalyst, selection temperature section (100 DEG C~
300 DEG C) a temperature spot, NO conversion ratio in 100 hours, under the temperature range studied, catalytic activity still maintains high
Stability, show high stability.
Embodiment 2
(1) by the H of natural smectite and 1.4mol/L2SO4Solution stirring in water bath 4.5 hours at 63 DEG C, wherein montmorillonite
With H2SO4The ratio of solution is 1g:10ml, the montmorillonite filtration washing after acidification to no SO4 2-Until (use BaCl2Solution inspection
Test), filtered sample 120 DEG C of dry 6h in drying box, ground 80 mesh sieve of mistake of sample after drying is modified up to acid
Montmorillonite.By the AlCl of 0.15mol/L3Aqueous solution and 0.15mol/LMnCl2Aqueous solution is with [Al3+]/[Mn2+] molar ratio=1:
The NaOH solution of 0.15mol/L is kept [OH by 0.3 mixing-]/[Al3++Mn2+] (molar ratio)=2.3, with the speed of 1mL/min
Degree is slowly dropped in above-mentioned solution, and temperature is kept for 65 DEG C, is subsequently agitated for 4 hours, resulting suspension aged at room temperature 16 is small
When, obtain aluminium manganese column liquid.Above-mentioned acidified modified montmorillonite is added according to a certain percentage in deionized water acidification is made and covers and be taken off
Stone suspension slurry, acidifying montmorillonite: deionized water (mass ratio)=1:50.The above aluminium manganese column liquid is added dropwise to acidification dropwise to cover
In de- stone suspension slurry, wherein ([Al3+]+[Mn2+]): acidifying montmorillonite=6mmol:1g keeps 63 DEG C of temperature stirrings 12 small
When, aged at room temperature 16 hours, 110 DEG C of drying and grinding sievings were then put it into Muffle furnace, with 2 DEG C/min heating rate liter
To 350 DEG C, this temperature section is kept to calcine 2 hours, gained sample is Al-Mn-PILC.By Eu (NO3)3It is molten in deionized water, be made into
Concentration is 0.002mol/L Eu (NO3)3Solution loads aluminium manganese pillared montmorillonite mass ratio (Eu wt%=1wt%) by Eu, meter
The praseodymium nitrate solution volume for calculating gained concentrations above is added in the above-mentioned aluminium manganese pillared montmorillonite of 4g, is slurried presoma, and 65
DEG C stirring 2h, rotary evaporated to dryness is dry, 105 DEG C drying 16 hours, 400 DEG C of roasting 2h, obtained support type Eu/Al-Mn-PILC is answered
Close catalyst.
(2) catalyst of the present invention, in the case where reaction pressure is normal pressure 1atm, high-speed 40,000h-1、O2Concentration 6vl.%,
H2O content 3vl.%, NH3Concentration is that 550ppm, NO concentration are 500ppm and N2Under the conditions of Balance Air, in wide temperature model
It encloses in (100 DEG C~300 DEG C), it is active (NO conversion ratio=15%~88%) with high catalytic removal low concentration of NO；It is reacting
Pressure is 40,000h under normal pressure 1atm, high-speed-1、O2Concentration 6vl.%, H2O content 3vl.%, NH3Concentration is 550ppm, NO
Concentration is 500ppm and N2Under the conditions of Balance Air, the compound Eu/Al-Mn-PILC catalyst of support type is investigated, chooses temperature section
One temperature spot of (100 DEG C~300 DEG C), NO conversion ratio in 100 hours, under the temperature range studied, catalytic activity is still
High stability is so kept, high stability is shown.
Embodiment 3
(1) by the H of natural smectite and 1.6mol/L2SO4Solution stirring in water bath 5 hours at 66 DEG C, wherein montmorillonite with
H2SO4The ratio of solution is 1g:10ml, the montmorillonite filtration washing after acidification to no SO4 2-Until (use BaCl2Solution is examined),
Filtered sample 120 DEG C of dry 6h in drying box, ground 80 mesh sieve of mistake of sample after drying take off up to modified cover of acid
Stone.By the AlCl of 0.25mol/L3Aqueous solution and 0.25mol/LMnCl2Aqueous solution is with [Al3+]/[Mn2+] molar ratio=1:0.5 is mixed
It closes, the NaOH solution of 0.25mol/L is slowly dropped in above-mentioned solution with the speed of 1mL/min, keep [OH-]/[Al3++
Mn2+] (molar ratio)=2.6, temperature keep 68 DEG C, be subsequently agitated for 5 hours, resulting suspension aged at room temperature 20 hours obtains
Aluminium manganese column liquid.Above-mentioned acidified modified montmorillonite is added according to a certain percentage in deionized water, acidifying montmorillonite suspension is made
Slurries, acidifying montmorillonite: deionized water (mass ratio)=1:60.The above aluminium manganese column liquid is added dropwise to acidifying montmorillonite dropwise to hang
In laitance liquid, wherein ([Al3+]+[Mn2+]): acidifying montmorillonite=8mmol:1g keeps 66 DEG C of temperature to stir 14 hours, room temperature
Aging 20 hours, 120 DEG C of drying and grinding sievings then put it into Muffle furnace, rise to 400 DEG C with 2 DEG C/min heating rate,
This temperature section is kept to calcine 3 hours, gained sample is Al-Mn-PILC.By Eu (NO3)3It is molten in deionized water, being made into concentration is
0.005mol/L Eu(NO3)3With Ce (NO3)3Solution loads aluminium manganese pillared montmorillonite weight ratio (Eu wt%=2wt%) by Eu
Aluminium manganese pillared montmorillonite mass ratio (Ce wt%=0.7wt%) is loaded with Ce, calculates the praseodymium nitrate and nitric acid of gained concentrations above
Cerium liquor capacity is added in the above-mentioned aluminium manganese pillared montmorillonite of 4g, is slurried presoma, 70 DEG C of stirring 3h, rotary evaporated to dryness
It is dry, 110 DEG C drying 20 hours, 400 DEG C of roasting 3h, be made support type Eu-Ce/Al-Mn-PILC-I composite catalyst.
(2) catalyst of the present invention is normal pressure 1atm in reaction pressure, 80,000h under air speed-1、O2Concentration 8vl.%, height
H2O content 6vl.%, NH3Concentration is that 770ppm, NO concentration are 700ppm and N2Under the conditions of Balance Air, in wide temperature model
It encloses in (100 DEG C~300 DEG C), catalytic removal low concentration of NO with higher is active (NO conversion ratio=20%~94%)；Anti-
Answer pressure for normal pressure 1atm, 80,000h under air speed-1、O2Concentration 8vl.%, H2O content 6vl.%, NH3Concentration is 770ppm, NO
Concentration is 700ppm and N2Under the conditions of Balance Air, support type Eu-Ce/Al-Mn-PILC-I catalyst is investigated, compared with low temperature
A temperature spot of section (100 DEG C~300 DEG C) is spent, NO conversion ratio in 100 hours, under the temperature range studied, catalysis is lived
Property still maintains high stability, shows high stability.
Embodiment 4
(1) by the H of natural smectite and 1.8mol/L2SO4Solution stirring in water bath 6 hours at 70 DEG C, wherein montmorillonite with
H2SO4The ratio of solution is 1g:10ml, the montmorillonite filtration washing after acidification to no SO4 2-Until (use BaCl2Solution is examined),
Filtered sample 120 DEG C of dry 6h in drying box, ground 80 mesh sieve of mistake of sample after drying take off up to modified cover of acid
Stone.By the AlCl of 0.3mol/L3Aqueous solution and 0.3mol/LMnCl2Aqueous solution is with [Al3+]/[Mn2+] molar ratio=1:0.6 is mixed
It closes, by the NaOH solution of 0.3mol/L, keeps [OH-]/[Al3++Mn2+] (molar ratio)=3, it is slowly dripped with the speed of 1mL/min
It is added in above-mentioned solution, temperature is kept for 70 DEG C, is subsequently agitated for 6 hours, resulting suspension aged at room temperature 24 hours obtains aluminium manganese
Column liquid.Above-mentioned acidified modified montmorillonite is added according to a certain percentage in deionized water, acidifying montmorillonite suspension slurry is made
Liquid, acidifying montmorillonite: deionized water (mass ratio)=1:80.The above aluminium manganese column liquid is added dropwise to acidifying montmorillonite dropwise to suspend
In slurries, wherein ([Al3+]+[Mn2+]): acidifying montmorillonite=10mmol:1g keeps 70 DEG C of temperature to stir 16 hours, and room temperature is old
Change 24 hours, 120 DEG C of drying and grinding sievings then put it into Muffle furnace, rise to 450 DEG C with 2 DEG C/min heating rate, protect
Hold this temperature section calcining 4 hours, gained sample is Al-Mn-PILC.By Eu (NO3)3It is molten in deionized water, being made into concentration is
0.008mol/L Eu(NO3)3With Ce (NO3)3Solution loads aluminium manganese pillared montmorillonite weight ratio (Eu wt%=by Eu
3wt%), Ce load aluminium manganese pillared montmorillonite mass ratio (Ce wt%=1wt%), calculate gained concentrations above praseodymium nitrate and
Cerous nitrate solution volume is added in the above-mentioned aluminium manganese pillared montmorillonite of 4g, is slurried presoma, 75 DEG C of stirring 4h, rotary evaporation
To drying, 120 DEG C drying 24 hours, 400 DEG C of roasting 4h, support type Eu-Ce/Al-Mn-PILC-II composite catalyst is made.
(2) catalyst of the present invention is normal pressure 1atm in reaction pressure, 100,000h under air speed-1、O2Concentration 10vl.%, height
H2O content 10vl.%, NH3Concentration is that 1100ppm, NO concentration are 1000ppm and N2Under the conditions of Balance Air, in lower temperature
It spends in range (100 DEG C~300 DEG C), catalytic removal low concentration of NO with higher is active (NO conversion ratio=18%~91%)；
It is normal pressure 1atm in reaction pressure, 100,000h under air speed-1、O2Concentration 10vl.%, H2O content 10vl.%, NH3Concentration is
1100ppm, NO concentration are 1000ppm and N2Under the conditions of Balance Air, Eu-Ce/Al-Mn-PILC-II catalyst, choosing are investigated
A temperature spot of temperature section (100 DEG C~300 DEG C) is taken, NO conversion ratio is urged under the temperature range studied in 100 hours
Change activity and still maintain high stability, shows high stability.
Claims (5)
1. a kind of aluminium manganese is total to pillared montmorillonite load Eu-Ce composite catalyst, which is characterized in that rare earth element Eu and Ce are born jointly
It is loaded in aluminium manganese to be total on pillared montmorillonite carrier, it is that compound hydroxy Al manganese solution is inserted into acidification and is covered to take off that aluminium manganese, which is total to pillared montmorillonite,
A kind of composite material between rock layers.
2. aluminium manganese as described in claim 1 is total to pillared montmorillonite load Eu-Ce composite catalyst it is characterized in that, rare earth element
Eu-Ce is carried on that aluminium manganese is total to pillared montmorillonite BET specific surface area and total pore volume is respectively 110~160m2/ g and 0.240~
0.350cm3/g。
3. the preparation aluminium manganese as claimed in claim 1 is total to pillared montmorillonite load Eu-Ce composite catalyzing agent method, feature exists
In, comprising the following steps:
1) aluminium manganese is total to the preparation of pillared montmorillonite carrier
By the H of natural smectite and 1.2~1.8mol/L2SO4Solution stirring in water bath 4~6 hours at 60-70 DEG C, wherein covering de-
Stone and H2SO4The ratio of solution is 1g:10ml, the montmorillonite filtration washing after acidification to no SO4 2-Until, use BaCl2Solution inspection
It tests, filtered sample 120 DEG C of dry 6h in drying box, ground 80 mesh sieve of mistake of sample after drying is covered up to acid is modified
De- stone；
By the AlCl of 0.1~0.3mol/L3Aqueous solution and 0.1~0.2mol/LMnCl2Aqueous solution is with [Al3+]/[Mn2+] molar ratio
=1:0~0.6 is mixed, and the NaOH solution of 0.1~0.3mol/L is slowly dropped in above-mentioned solution with the speed of 1mL/min,
[OH-]/[Al3++Mn2+] molar ratio=2~3, temperature keep 60~70 DEG C, be subsequently agitated for 3~6 hours, resulting suspension
Aged at room temperature 12~24 hours, obtain aluminium manganese column liquid；
Above-mentioned acidified modified montmorillonite is added according to a certain percentage in deionized water, acidifying montmorillonite suspension slurry is made, acid
Change montmorillonite: mass ratio=1:40~80 of deionized water；The above aluminium manganese column liquid is added dropwise to acidifying montmorillonite dropwise to suspend
In slurries, wherein [Al3+]+[Mn2+]: acidifying montmorillonite=4~10mmol:1g keep 60~70 DEG C of temperature stirrings 10~16 small
When, aged at room temperature 12~24 hours, the sieving of 100~120 DEG C of drying and grindings was then put it into Muffle furnace, with 1~2 DEG C/
Min heating rate rises to 300~450 DEG C, this temperature section is kept to calcine 1~4 hour, and gained sample is aluminium manganese pillared montmorillonite；
2) rotary evaporation prepares aluminium manganese and is total to pillared montmorillonite load Eu-Ce composite catalyst
Aluminium manganese made above is total to pillared montmorillonite, 0.002mol/L~0.008mol/L Eu (NO is added3)3With Ce (NO3)3It is molten
In liquid, 60~75 DEG C of 1~4h of stirring, wherein aluminium manganese is total to pillared montmorillonite and Eu (NO3)3Ratio be 100g:0.006mol~
0.018mol, aluminium manganese are total to pillared montmorillonite and Ce (NO3)3Ratio is 100g:0.003mol~0.007mol rotary evaporated to dryness
It is dry, 100~120 DEG C of dryings 12~for 24 hours, composite catalyst is made in 400 DEG C of 1~4h of roasting.
4. the aluminium manganese described in claim 1 is total to pillared montmorillonite load Eu-Ce composite catalyst in the application for eliminating NO,
It is passed through it is characterized by: above-mentioned catalyst is placed in continuous flow fixed bed device containing 330ppm~1100ppmNH3、
300ppm~1000ppmNO, 5vl.%~10vl.%O2With 1vl.%~10vl.%H2It is reacted in the gaseous mixture of O, it is above
The remaining gas of gaseous mixture is inert gas；Reaction pressure is normal pressure 1atm, reaction velocity 10,000h-1~100,000h-1,
Reaction temperature is 100 DEG C~300 DEG C.
5. application according to claim 4, wherein in gaseous mixture, the concentration of all gas is final dense after gas mixing
Degree, concentration is all volumn concentration；NH in reaction gas3Concentration is greater than the concentration of NO, and concentration ratio is 1.0~1.2:1, instead
Answer the inert gas He or N in gas2。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811576278.8A CN109589969A (en) | 2018-12-22 | 2018-12-22 | Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Eu-Ce composite catalyst |
| CN201910332203.3A CN110013846B (en) | 2018-12-22 | 2019-04-24 | Preparation method and application of aluminum-manganese co-pillared montmorillonite-loaded Ce-Cu or Eu-Ce composite catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811576278.8A CN109589969A (en) | 2018-12-22 | 2018-12-22 | Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Eu-Ce composite catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109589969A true CN109589969A (en) | 2019-04-09 |
Family
ID=65963813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811576278.8A Pending CN109589969A (en) | 2018-12-22 | 2018-12-22 | Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Eu-Ce composite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109589969A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111250078A (en) * | 2020-04-10 | 2020-06-09 | 江西农业大学 | MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof |
| CN111375407A (en) * | 2020-01-08 | 2020-07-07 | 上海电力大学 | Low-temperature denitration catalyst and preparation method and application thereof |
| CN113648990A (en) * | 2021-08-17 | 2021-11-16 | 北京工业大学 | Preparation method and application of iron pillared montmorillonite-loaded Mn-Ce-Sm composite catalyst |
-
2018
- 2018-12-22 CN CN201811576278.8A patent/CN109589969A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111375407A (en) * | 2020-01-08 | 2020-07-07 | 上海电力大学 | Low-temperature denitration catalyst and preparation method and application thereof |
| CN111375407B (en) * | 2020-01-08 | 2022-06-21 | 上海电力大学 | Low-temperature denitration catalyst and preparation method and application thereof |
| CN111250078A (en) * | 2020-04-10 | 2020-06-09 | 江西农业大学 | MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof |
| CN111250078B (en) * | 2020-04-10 | 2020-11-20 | 江西农业大学 | MnOx @ Eu-CeOx low-temperature SCR flue gas denitration catalyst and preparation method and application thereof |
| CN113648990A (en) * | 2021-08-17 | 2021-11-16 | 北京工业大学 | Preparation method and application of iron pillared montmorillonite-loaded Mn-Ce-Sm composite catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deng et al. | Strontium-doped lanthanum cobaltite and manganite: highly active catalysts for toluene complete oxidation | |
| Chen et al. | Enhanced activity of tungsten modified CeO2/TiO2 for selective catalytic reduction of NOx with ammonia | |
| Cao et al. | Influence of phosphorus on the NH3-SCR performance of CeO2-TiO2 catalyst for NOx removal from co-incineration flue gas of domestic waste and municipal sludge | |
| KR101990156B1 (en) | METHOD FOR TREATING A GAS CONTAINING NITROGEN OXIDES(NOx), IN WHICH A COMPOSITION COMPRISING CERIUM OXIDE AND NIOBIUM OXIDE IS USED AS A CATALYST | |
| CN107456981B (en) | A kind of exhaust gas denitration composite catalyst and preparation method thereof | |
| Shen et al. | Deactivation mechanism of potassium additives on Ti 0.8 Zr 0.2 Ce 0.2 O 2.4 for NH 3-SCR of NO | |
| CN105833901B (en) | A kind of PrOx-MnOx/ SAPO-34 low-temperature SCR catalyst for denitrating flue gas and the preparation method and application thereof | |
| CN111450841A (en) | Reduction method simultaneous desulfurization and denitrification catalyst prepared from red mud and preparation method thereof | |
| CN102294248A (en) | Fe-Mn composite oxide catalyst for denitration and demercuration at the same time and preparation method thereof | |
| KR101629483B1 (en) | Vanadium-based denitration catalyst and preparing method of the same | |
| Zhang et al. | Novel promoting effects of tungsten on the selective catalytic reduction of NO by NH3 over MnOx–CeO2 monolith catalyst | |
| CN109589969A (en) | Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Eu-Ce composite catalyst | |
| MXPA06005460A (en) | Exhaust gas catalyst. | |
| CN104722292A (en) | Halloysite/lanthanon perovskite composite SCR catalyst and preparation method thereof | |
| CN105396579A (en) | Fire coal flue gas denitration demercuration catalyst and preparation method and application thereof | |
| CN109603807B (en) | Modified activated carbon Ce-Nb/TiO2@ AC low-temperature efficient desulfurization and denitrification catalyst and preparation method thereof | |
| CN104923213B (en) | A kind of nontoxic rare-earth type denitrating catalyst and its preparation method and application | |
| CN105413715A (en) | Composite support loaded type sulfated Mn-Co-Ce sulfur-tolerant catalyst for low-temperature flue gas denitration and preparation method of sulfur-tolerant catalyst | |
| CN106975513A (en) | A kind of support type tourmaline rare earth is combined selective denitrification catalyst | |
| CN108393085A (en) | A kind of attapulgite load cerium dopping MnTiOXTernary component low-temperature denitration catalyst and preparation method | |
| CN109603808A (en) | The preparation method and application of zirconium pillared montmorillonite load C e-Nb composite catalyst | |
| Ye et al. | Synthesis of manganese ore/Co3O4 composites by sol–gel method for the catalytic oxidation of gaseous chlorobenzene | |
| WU et al. | Effect of preparation methods on denitration performance of V-Mo/TiO2 catalyst | |
| CN105817229A (en) | Rare earth element modified load type cobaltosic oxide catalyst and preparation method thereof | |
| Jun et al. | Structure and properties of amorphous CeO2@ TiO2 catalyst and its performance in the selective catalytic reduction of NO with NH3 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190409 |
|
| WD01 | Invention patent application deemed withdrawn after publication |