CN110773149A - Preparation method of high-specific-surface-area aluminum-manganese SCR catalyst - Google Patents
Preparation method of high-specific-surface-area aluminum-manganese SCR catalyst Download PDFInfo
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- CN110773149A CN110773149A CN201910899393.7A CN201910899393A CN110773149A CN 110773149 A CN110773149 A CN 110773149A CN 201910899393 A CN201910899393 A CN 201910899393A CN 110773149 A CN110773149 A CN 110773149A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- -1 aluminum-manganese Chemical compound 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 239000011363 dried mixture Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000003546 flue gas Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical group [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000373 fatty alcohol group Chemical group 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 32
- 239000007789 gas Substances 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (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)
Abstract
The invention discloses a preparation method of an aluminum-manganese SCR catalyst with a high specific surface area. The method comprises the following steps: dissolving a surfactant, organic carboxylic acid and inorganic acid in an ethanol solution, adding an aluminum source while stirring, keeping the temperature at 30-55 ℃, and continuously stirring for 10-20 hours; drying the mixture obtained by the reaction at the temperature of 40-80 ℃ for 30-50 hours; then roasting the dried mixture at 400-600 ℃ for 4-8 hours; dipping the obtained product in an aqueous solution containing organic carboxylic acid, manganese salt and aluminum source, stirring for 5-15 hours, and then drying in an oven at 105 ℃ for 3-5 hours; calcining the obtained mixture at the temperature of 500-700 ℃ for 90-240 minutes to obtain the high specific surface area aluminum-manganese low-temperature SCR catalyst. The invention has the advantages of simple operation process, short preparation time, low cost, easy industrial amplification and the like.
Description
Technical Field
The invention belongs to the technical field of flue gas denitration catalysts, and particularly relates to a preparation method of an aluminum-manganese SCR catalyst with a high specific surface area.
Background
The main hazards of nitrogen oxides (NOx) are: damage to the human body; forming acid rain and acid mist; forming photochemical smog with CxHy; and destroying the ozone layer. NOx is mainly derived from fuel combustion processes and various industrial processes, while the amount of flue gas discharged from coal-fired boilers and the like is large, and in which NOx of 90% or more is present as NO which is hardly soluble in water, control is relatively difficult.
Along with the development of social economy in China, the energy consumption and the environmental pollution are increasingly serious, and the emission of NOx is high due to the energy structure mainly comprising coal in China. The emission amount of nitrogen oxides of coal-fired power plants, industrial kilns and motor vehicles is the main emission source of three nitrogen oxides in China and is also the three main markets for the development of the denitration industry in China in future. In order to control the emission of nitrogen oxides, the national nitrogen oxide emission policy standards are becoming stricter.
Among the various flue gas denitration methods, the Selective Catalytic Reduction (SCR) method is the most widely commercially used flue gas denitration technology at present, wherein the preparation and production of the catalyst are the most important parts, and the catalytic performance of the catalyst directly influences the overall denitration effect of the SCR. At present, the SCR denitration catalyst currently used in China mainly comprises titanium dioxide loaded active components of vanadium pentoxide and tungsten oxide (V)
2O
5-WO
3-TiO
2) Although the vanadium-based catalyst has stable denitration activity and performance, the activity temperature is higher between 300 and 400 ℃, and an SCR denitration reactor is required to be arranged atThe flue gas temperature of the boiler can be effectively utilized between the economizer and the air preheater, and in addition, the phenomena of pore channel blockage and poisoning of the catalyst are easily caused by fly ash and high sulfur content in the flue gas. Therefore, the research and development of the low-temperature denitration catalyst adopt the low-temperature SCR technology, the SCR reactor can be arranged behind the dust removal and desulfurization device, the denitration energy consumption is reduced, and the phenomena of pore channel blockage and poisoning of the catalyst in the use process can be avoided, so that the research and development of the catalyst are increasingly paid attention by people.
Disclosure of Invention
The invention aims to provide a preparation method of an aluminum-manganese SCR catalyst with a high specific surface area. The invention has the advantages of simple operation process, short preparation time, low cost, easy industrial amplification and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an aluminum-manganese SCR catalyst with a high specific surface area comprises the following steps:
(1) dissolving a surfactant, organic carboxylic acid and inorganic acid in an ethanol solution, adding an aluminum source while stirring, keeping the temperature at 30-55 ℃, and continuously stirring for 10-20 hours;
(2) drying the mixture obtained by the reaction at the temperature of 40-80 ℃ for 30-50 hours;
(3) then roasting the dried mixture at 400-600 ℃ for 4-8 hours;
(4) dipping the product obtained in the step (3) in an aqueous solution containing organic carboxylic acid, manganese salt and an aluminum source, stirring for 5-15 hours, and then drying in an oven at 105 ℃ for 3-5 hours;
(5) and (4) calcining the mixture obtained in the step (4) at the temperature of 500-700 ℃ for 90-240 minutes to obtain the high specific surface area aluminum manganese low-temperature SCR catalyst.
Further, in the above production method, the aluminum source: manganese salt: organic carboxylic acid: inorganic acid: ethanol: deionized water: the molar ratio of the surface active agent is (2-50): (0.5-2.5): (1-30): (10-120): (5-50): (1-10): 1.
further, in the above production method, the surfaceThe active agent is a nonionic surfactant; preferably, the nonionic surfactant is fatty alcohol-polyoxyethylene ether; more preferably, the molecular formula of the fatty alcohol-polyoxyethylene ether is C
12H
25O(C
2H
4O)
nH, wherein: n is 3-9.
Further, in the above preparation method, the aluminum source is aluminum sec-butoxide, aluminum isopropoxide, sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate.
Further, in the above preparation method, the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
Further, in the above preparation method, the organic carboxylic acid is salicylic acid, citric acid, glacial acetic acid, malic acid, gluconic acid, or lauric acid.
Further, in the above preparation method, the manganese salt is a sulfate, a hydrochloride or a nitrate of manganese.
Further, in the preparation method, the specific surface area of the high specific surface area aluminum manganese SCR catalyst is 500-600m
2/g。
Further, in the preparation method, when the high specific surface area aluminum manganese SCR catalyst is used for flue gas denitration, ammonia gas is used as a reducing agent, flue gas to be treated containing NO with equal concentration is introduced, and the conversion rate of NO is not lower than 98% when the reaction temperature is 190-270 ℃.
The invention has the following technical characteristics:
1) the prepared denitration catalyst material has high specific surface area, increases the contact area of reaction gas and active components, and is beneficial to the efficient reaction;
2) the preparation process is simple and easy to implement and easy to industrially amplify;
3) the surfactant, active components of manganese oxide and organic carboxylic acid additive are cheap and easy to obtain, and the environment is friendly;
4) ammonia gas is used as a reducing agent, the flue gas to be treated containing NO with equal concentration is introduced, and the conversion rate of NO is not lower than 98% when the reaction temperature is 190-270 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1:
2g of fatty alcohol-polyoxyethylene ether, 0.6g of citric acid and 0.18g of manganese nitrate were added to 30mL of an ethanol solution containing 2.0g of 12M hydrochloric acid, the mixture was stirred at room temperature to completely dissolve the surfactant, 3.06g of aluminum isopropoxide was simultaneously added to the system, and after stirring at 35 ℃ for 24 hours, the reaction mixture was poured into a petri dish and treated at 50 ℃ for 24 hours, and then the sample was baked at 400 ℃ for 5 hours. Taking out, soaking in 1.55g of citric acid and 1.8g of manganese nitrate solution, stirring, drying in a 105 ℃ oven, and finally carrying out high-temperature 550 ℃ heat treatment on the mixture to obtain the high-specific-surface-area aluminum manganese low-temperature SCR catalyst.
Method for testing activity of catalyst
0.3g of the catalyst sample after passing through a 50 mesh sieve was charged into a reaction tube, and the temperature was programmed by a tube-type resistance furnace. The mixed gas simulates smoke and is provided by a corresponding steel cylinder. The proportion (volume fraction) of the corresponding mixed gas is as follows: the simulated smoke composition is 0.05 percent of NO and 0.05 percent of NH
3Ar is balance gas, GHSV is 40000h
-1The calculation formula of the nitrogen oxide removal rate is as follows:
wherein NO
inIndicating the concentration of NO in the gas inlet before the catalytic reaction, NO
outIndicating the NO concentration at the outlet after the catalytic reaction. The outlet gas NO content was analyzed and the denitration efficiency X was calculated, the results are shown in table 1:
TABLE 1NO conversion
From the above verification example, it can be seen that the conversion rate of NO of the SCR flue gas denitration catalyst of the present invention is not lower than 98% under the flue gas temperature condition of 190-270 ℃.
Example 2:
1.5g of fatty alcohol-polyoxyethylene ether, 0.75g of citric acid and 0.45g of manganese chloride were added to 30mL of an ethanol solution containing 2.0g of 12M hydrochloric acid, the mixture was stirred at room temperature to completely dissolve the surfactant, 3.06g of aluminum isopropoxide was simultaneously added to the system, the mixture was stirred at 35 ℃ for 24 hours, the reaction mixture was poured into a petri dish and treated at 50 ℃ for 24 hours, and then the sample was baked at 400 ℃ for 5 hours. Taking out, soaking in 1.8g of citric acid and 2.5g of manganese nitrate solution, stirring, drying in a 105 ℃ oven, and finally carrying out high-temperature 550 ℃ heat treatment on the mixture to obtain the high-specific-surface-area aluminum manganese low-temperature SCR catalyst.
Method for testing activity of catalyst
0.3g of the catalyst sample after passing through a 50 mesh sieve was charged into a reaction tube, and the temperature was programmed by a tube-type resistance furnace. The mixed gas simulates smoke and is provided by a corresponding steel cylinder. The proportion (volume fraction) of the corresponding mixed gas is as follows: the simulated smoke composition is 0.05 percent of NO and 0.05 percent of NH
3Ar is balance gas, GHSV is 40000h
-1The calculation formula of the nitrogen oxide removal rate is as follows:
wherein NO
inIndicating the concentration of NO in the gas inlet before the catalytic reaction, NO
outIndicating the NO concentration at the outlet after the catalytic reaction. The outlet gas NO content was analyzed and the denitration efficiency X was calculated, the results are shown in table 2:
TABLE 2NO conversion
From the above verification example, it can be seen that the conversion rate of NO of the SCR flue gas denitration catalyst of the present invention is not lower than 98% under the flue gas temperature condition of 190-270 ℃.
Example 3:
1.8g of fatty alcohol-polyoxyethylene ether, 0.55g of citric acid and 0.45g of manganese nitrate were added to 30mL of an ethanol solution containing 2.0g of 12M hydrochloric acid, the mixture was stirred at room temperature to completely dissolve the surfactant, 3.06g of aluminum isopropoxide was simultaneously added to the system, the mixture was stirred at 35 ℃ for 24 hours, the reaction mixture was poured into a petri dish and treated at 50 ℃ for 24 hours, and then the sample was baked at 400 ℃ for 5 hours. Taking out, soaking the mixture in 2.0g of citric acid and 2.5g of manganese nitrate solution, stirring, drying in a 105 ℃ oven, and finally carrying out high-temperature 550 ℃ heat treatment on the mixture to obtain the high-specific-surface-area aluminum manganese low-temperature SCR catalyst.
Method for testing activity of catalyst
0.3g of the catalyst sample after passing through a 50 mesh sieve was charged into a reaction tube, and the temperature was programmed by a tube-type resistance furnace. The mixed gas simulates smoke and is provided by a corresponding steel cylinder. The proportion (volume fraction) of the corresponding mixed gas is as follows: the simulated smoke composition is 0.05 percent of NO, 0.05 percent of NH3, Ar is balance gas, GHSV is 40000h-1, and the calculation formula of the removal rate of nitrogen oxides is as follows:
wherein NO
inIndicating the concentration of NO in the gas inlet before the catalytic reaction, NO
outIndicating the NO concentration at the outlet after the catalytic reaction. The outlet gas NO content was analyzed and the denitration efficiency X was calculated, the results are shown in table 3:
TABLE 3NO conversion
From the above verification example, it can be seen that the conversion rate of NO of the SCR flue gas denitration catalyst of the present invention is not lower than 98% under the flue gas temperature condition of 190-270 ℃.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of an aluminum-manganese SCR catalyst with a high specific surface area is characterized by comprising the following steps:
(1) dissolving a surfactant, organic carboxylic acid and inorganic acid in an ethanol solution, adding an aluminum source while stirring, keeping the temperature at 30-55 ℃, and continuously stirring for 10-20 hours;
(2) drying the mixture obtained by the reaction at the temperature of 40-80 ℃ for 30-50 hours;
(3) then roasting the dried mixture at 400-600 ℃ for 4-8 hours;
(4) dipping the product obtained in the step (3) in an aqueous solution containing organic carboxylic acid, manganese salt and an aluminum source, stirring for 5-15 hours, and then drying in an oven at 105 ℃ for 3-5 hours;
(5) and (4) calcining the mixture obtained in the step (4) at the temperature of 500-700 ℃ for 90-240 minutes to obtain the high specific surface area aluminum manganese low-temperature SCR catalyst.
2. The method for preparing the high specific surface area aluminum manganese SCR catalyst according to claim 1, wherein the aluminum source: manganese salt: organic carboxylic acid: inorganic acid: ethanol: deionized water: the molar ratio of the surface active agent is (2-50): (0.5-2.5): (1-30): (10-120): (5-50): (1-10): 1.
3. the method for preparing the high specific surface area aluminum manganese SCR catalyst according to claim 1, wherein the surfactant is a nonionic surfactant.
4. The method for preparing the high specific surface area aluminum manganese SCR catalyst according to claim 3, wherein the non-ionic surfactant is fatty alcohol polyoxyethylene ether.
5. The method for preparing the high specific surface area aluminum manganese SCR catalyst according to claim 1, wherein the aluminum source is aluminum sec-butoxide, aluminum isopropoxide, sodium metaaluminate, aluminum nitrate, aluminum chloride or aluminum sulfate.
6. The method for preparing the high specific surface area aluminum manganese SCR catalyst according to claim 1, wherein the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
7. The method for preparing the high specific surface area aluminum manganese SCR catalyst as recited in claim 1, wherein the organic carboxylic acid is salicylic acid, citric acid, glacial acetic acid, malic acid, gluconic acid or lauric acid.
8. The method for preparing the high specific surface area aluminum manganese SCR catalyst according to claim 1, wherein the manganese salt is a sulfate, a hydrochloride or a nitrate of manganese.
9. The method as claimed in claim 1, wherein the specific surface area of the high specific surface area aluminum-manganese SCR catalyst is 500-600m
2/g。
10. The preparation method of the high specific surface area aluminum-manganese SCR catalyst as recited in claim 1, wherein when the high specific surface area aluminum-manganese SCR catalyst is used for denitration of flue gas, ammonia gas is used as a reducing agent, flue gas to be treated containing NO with equal concentration is introduced, and the conversion rate of NO is not lower than 98% when the reaction temperature is 190-270 ℃.
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