CN109589970A - Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Pr-Ce composite catalyst - Google Patents
Aluminium manganese is total to the preparation method and application of pillared montmorillonite load Pr-Ce composite catalyst Download PDFInfo
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- CN109589970A CN109589970A CN201811576298.5A CN201811576298A CN109589970A CN 109589970 A CN109589970 A CN 109589970A CN 201811576298 A CN201811576298 A CN 201811576298A CN 109589970 A CN109589970 A CN 109589970A
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- Prior art keywords
- montmorillonite
- total
- aluminium manganese
- catalyst
- pillared montmorillonite
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- 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 83
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 77
- -1 Aluminium manganese Chemical compound 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 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
- 239000007788 liquid Substances 0.000 claims description 17
- 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
- 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 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 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
- 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
- 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
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 239000012495 reaction gas 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 2
- 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 13
- 229910002651 NO3 Inorganic materials 0.000 description 12
- 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
- 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
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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)
- Exhaust Gas Treatment By Means Of Catalyst (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 Pr-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 mixed solution and aluminium manganese and 1~4 hour, rotary evaporation drying is mixed, roasting is made aluminium manganese and is total to pillared montmorillonite load Pr-Ce composite catalyst.There is catalyst of the present invention big specific surface area, orderly aluminium manganese delaminated structure and Pr 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 cheap process of the present invention 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 Pr-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, and system is than 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 Pr-Ce/Al-Mn-PILC composite catalyst by rotary evaporation,
Obtain the catalysis NO activity in good low temperature range (100 DEG C~300 DEG C) and high stability.Just had been reported that at present
Document from the point of view of, it is most of using independent pillared method and to load although other pillared montmorillonites also have preferable activity
Rare earth element prepares catalyst, and reaction temperature is relatively narrow, and activity is poor, and Pr-Ce/Al-Mn-PILC prepared by this patent is catalyzed
Agent has preferable activity under cryogenic.The implementation of this project obtains: project of national nature science fund project (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 the preparations that a kind of aluminium manganese is total to the pillared montmorillonite load compound composite catalyst of Pr-Ce
And its it is used for catalytic removal NO pollutant.The BET specific surface area volume of montmorillonite is 48m2The aluminium manganese of/g, Pr-Ce load is pillared
For the BET specific surface area of montmorillonite compared with montmorillonite original soil, increase is very big, is 141m2/g.Provided catalyst can be lower
Reaction temperature (100 DEG C~300 DEG C) under, efficiently eliminate NO (20%~94% NO conversion ratio).Moreover, this catalyst has
Higher 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 the pillared montmorillonite load compound composite catalyst of Pr-Ce
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
0.019mol/L~0.022mol/LPr (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 Pr (NO3)3Ratio is 100g:0.014mol~0.058mol, 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 Pr-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 Pr-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, Pr/Al-Mn-PILC, Pr-Ce/Al- prepared by the embodiment of the present invention 1,2,3 and 4
The XRD diagram of Mn-PILC-I, Pr-Ce/Al-Mn-PILC-II catalyst.
Fig. 2 is Ce/Al-Mn-PILC, Pr/Al-Mn-PILC, Pr-Ce/Al- prepared by the embodiment of the present invention 1,2,3 and 4
The N of Mn-PILC-I, Pr-Ce/Al-Mn-PILC-II catalyst2Absorption/desorption figure.
Fig. 3 is Ce/Al-Mn-PILC, Pr/Al-Mn-PILC, Pr-Ce/Al- prepared by the embodiment of the present invention 1,2,3 and 4
NH on Mn-PILC-I, Pr-Ce/Al-Mn-PILC-II catalyst3Selective Catalytic Reduction of NO activity.
Fig. 4 is Ce/Al-Mn-PILC, Pr/Al-Mn-PILC, Pr-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, Pr-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
0.019mol/L solution loads aluminium manganese pillared montmorillonite mass ratio (Ce wt%=1wt%) by Ce, calculates gained concentrations above
Cerous nitrate solution volume be added in the above-mentioned aluminium manganese pillared montmorillonite of 4g, be slurried presoma, 60 DEG C of stirring 1h, rotation is steamed
Be sent 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 Pr (NO3)3It is molten in deionized water, be made into
Concentration is 0.019mol/L Pr (NO3)3Solution loads aluminium manganese pillared montmorillonite mass ratio (Pr wt%=4wt%) by Pr, 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 Pr/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=14%~87%) 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 Pr/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 Pr (NO3)3It is molten in deionized water, being made into concentration is
0.021mol/L Pr(NO3)3Solution loads aluminium manganese pillared montmorillonite weight ratio (Pr wt%=6wt%) by Pr, and Ce loads aluminium
The praseodymium nitrate solution volume that manganese pillared montmorillonite mass ratio (Ce wt%=2wt%) calculates gained concentrations above is added on 4g
State in aluminium manganese pillared montmorillonite, be slurried presoma, 70 DEG C of stirring 3h, rotary evaporated to dryness is dry, 110 DEG C drying 20 hours,
Support type Pr-Ce/Al-Mn-PILC-I composite catalyst is made in 400 DEG C of roasting 3h.
(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=19%~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 Pr-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 Pr (NO3)3It is molten in deionized water, being made into concentration is
0.022mol/L Pr(NO3)3With Ce (NO3)3Solution loads aluminium manganese pillared montmorillonite weight ratio (Pr wt%=by Pr
8wt%), Ce loads the praseodymium nitrate and nitre that aluminium manganese pillared montmorillonite mass ratio (Ce wt%=3wt%) calculates gained concentrations above
Sour cerium liquor capacity is added in the above-mentioned aluminium manganese pillared montmorillonite of 4g, is slurried presoma, 75 DEG C of stirring 4h, rotary evaporation is extremely
It is dry, 120 DEG C drying 24 hours, 400 DEG C of roasting 4h, obtained support type Pr-Ce/Al-Mn-PILC-II composite catalyst.
(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=17%~90%)；
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, Pr-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 Pr-Ce composite catalyst, which is characterized in that rare earth element Pr 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 montmorillonite layer that aluminium manganese, which is total to pillared montmorillonite,
Between a kind of composite material.
2. as claimed in claim 1 aluminium manganese is total to pillared montmorillonite load Pr-Ce composite catalyst, which is characterized in that rare earth member
Plain Pr-Ce is carried on that aluminium manganese is total to pillared montmorillonite BET specific surface area and total pore volume is respectively 120~150m2/ g and 0.250~
0.342cm3/g。
3. the method that the aluminium manganese of preparation as claimed in claim 1 described 1 is total to pillared montmorillonite load Pr-Ce composite catalyst, special
Sign is, 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
Liquid 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 preparation Pr-Ce load aluminium manganese is total to pillared montmorillonite
Aluminium manganese made above is total to pillared montmorillonite, 0.019mol/L~0.022mol/L Pr (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 Pr (NO3)3Ratio be 100g:0.014mol~
0.058mol, aluminium manganese are total to pillared montmorillonite and Ce (NO3)3Ratio is 100g:0.007mol~0.021mol, rotary evaporated to dryness
It is dry, 100~120 DEG C of dryings 12~for 24 hours, support type Pr-Ce/Al-Mn-PILC composite catalyst is made in 400 DEG C of 1~4h of roasting.
4. the compound Pr-Ce/Al-Mn-PILC catalyst of support type described in claim 1 is in the application for eliminating NO, feature exists
In: above-mentioned catalyst is placed in continuous flow fixed bed device and is passed through containing 330ppm~1100ppmNH3, 300ppm~
1000ppmNO, 5vl.%~10vl.%O2With 1vl.%~10vl.%H2It is reacted in the gaseous mixture of O, the above gaseous mixture
Remaining gas is inert gas；Reaction pressure is normal pressure 1atm, reaction velocity 10,000h-1~100,000h-1, reaction temperature
It is 100 DEG C~300 DEG C.
5. application according to claim 3, wherein the concentration of all gas is final dense after gas mixing in gaseous mixture
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。
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| CN103706353A (en) * | 2013-12-19 | 2014-04-09 | 绍兴文理学院 | AlMn composite pillared clay supported CrCe catalyst, and preparation method and application of catalyst |
| CN105664838A (en) * | 2016-03-28 | 2016-06-15 | 中国科学院过程工程研究所 | Demercuration adsorbent based on pillared montmorillonite, preparation method and application thereof |
| CN108452796A (en) * | 2018-03-12 | 2018-08-28 | 北京科技大学 | A kind of preparation method of the modified montmorillonite used base SCR denitration of Supported Manganese and cerium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103706353A (en) * | 2013-12-19 | 2014-04-09 | 绍兴文理学院 | AlMn composite pillared clay supported CrCe catalyst, and preparation method and application of catalyst |
| CN105664838A (en) * | 2016-03-28 | 2016-06-15 | 中国科学院过程工程研究所 | Demercuration adsorbent based on pillared montmorillonite, preparation method and application thereof |
| CN108452796A (en) * | 2018-03-12 | 2018-08-28 | 北京科技大学 | A kind of preparation method of the modified montmorillonite used base SCR denitration of Supported Manganese and cerium |
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