CN109482223B - Coal ash-based denitration catalyst, preparation method thereof and denitration method - Google Patents
Coal ash-based denitration catalyst, preparation method thereof and denitration method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000010883 coal ash Substances 0.000 title description 4
- 239000002808 molecular sieve Substances 0.000 claims abstract description 107
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000010881 fly ash Substances 0.000 claims abstract description 83
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000243 solution Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000003513 alkali Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000012452 mother liquor Substances 0.000 claims abstract description 22
- 238000004090 dissolution Methods 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 15
- -1 polyethylene Polymers 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 9
- 239000004698 Polyethylene Substances 0.000 claims abstract description 9
- 239000004743 Polypropylene Substances 0.000 claims abstract description 9
- 229920000573 polyethylene Polymers 0.000 claims abstract description 9
- 229920001155 polypropylene Polymers 0.000 claims abstract description 9
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 9
- 239000010413 mother solution Substances 0.000 claims abstract description 5
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 229910052681 coesite Inorganic materials 0.000 claims description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 229910052682 stishovite Inorganic materials 0.000 claims description 25
- 229910052905 tridymite Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000002440 industrial waste Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003546 flue gas Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 19
- 239000000843 powder Substances 0.000 description 17
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- 230000007935 neutral effect Effects 0.000 description 6
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000547 structure data Methods 0.000 description 3
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
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- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention relates to the field of utilization of fly ash, and discloses a fly ash-based denitration catalyst, a preparation method thereof and a denitration method. The method comprises the following steps: (1) mixing and dissolving the fly ash and the acid liquor, and filtering to obtain iron-removing liquid and iron-removing fly ash; (2) carrying out alkali dissolution reaction on the deironing fly ash and alkali liquor, and filtering to obtain desiliconized solution; (3) mixing the desiliconized solution with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and adjusting the pH value to acidity to obtain a synthetic mother solution; (4) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain an SBA-15 mesoporous molecular sieve; (5) and (3) soaking the SBA-15 mesoporous molecular sieve by using a cobalt nitrate solution and the iron removal liquid, and performing rotary evaporation by using ethanol to obtain the denitration catalyst. The denitration catalyst prepared from the fly ash can be realized, better catalytic performance is provided, and the denitration effect is improved.
Description
Technical Field
The invention relates to the field of utilization of fly ash, in particular to a fly ash-based denitration catalyst, a preparation method thereof and a denitration method.
Background
Coal plays a very important role in national economic development as fossil fuel. However, a large amount of fly ash waste discharged by coal combustion is increased year by year and is randomly stacked, so that a large amount of land resources are occupied, heavy metal pollution of underground water is caused, ecological balance is seriously damaged, and the environment is polluted. At present, the main method for treating the fly ash is brick making, and the fly ash is used as industrial fillers for bridge construction, paving, wall materials and the like, has the advantages of simple operation process, low technical requirement level, easy in-situ digestion and the like, but has lower added value.
CN103818920A discloses a method for preparing Si-Al ordered mesoporous molecular sieve, which comprises the following steps: extracting waste fly ash of a thermal power plant as a raw material to obtain a solution containing silicon and aluminum, adding ethanol and water into CTAB (cetyl trimethyl ammonium bromide) serving as a template agent, quickly synthesizing a pre-product at room temperature, placing the pre-product in a muffle furnace, calcining to remove the template agent, and cooling to obtain a product; wherein the mole ratio of CTAB, water, ethanol and the total amount of silicon and aluminum in the solution is (0.4-0.6): (300-500): (50-60): 1. further disclosed is: the silicon-aluminum source extraction is to mix the fly ash and NaOH, calcine the mixture for 1 to 2 hours at the temperature of 550 ℃ and 600 ℃, grind the mixture after cooling, mix the ground mixture with water, and separate out supernate as a silicon-aluminum source solution; and adding CTAB, water and ethanol into the silica-alumina source solution to obtain a mixed solution, adjusting the pH of the mixed solution to 9-10 by adopting acid, and stirring to obtain a white solid. The method for treating the fly ash by the method is an alkali fusion method, high-temperature calcination is needed, the energy consumption is large, and the process is not green; and the mesoporous molecular sieve is obtained by an acid regulation method, but not by a hydrothermal crystallization method.
CN103861556A discloses a preparation method of fly ash-based SBA-15, which comprises the following steps: (1) mixing the fly ash and alkali, melting and cooling to obtain a mixture; (2) adding water to the mixture for dissolving and filtering to obtain a supernatant; (3) dissolving a surfactant P123 in water, adjusting the pH value to be acidic, then aging, filtering, washing and drying; (4) and (4) roasting the material dried in the step (3) to obtain a powdery material fly ash-based SBA-15. Discloses that the pore volume of the obtained mesoporous material is 0.6-0.9cm3Specific surface area of 370-3Per g, the aperture is 5-8 nm; it is not disclosed whether the composition of the mesoporous material contains aluminum or not, and whether the material has a microporous structure or not. The fly ash is treated by an alkali fusion method, high-temperature calcination is needed, energy consumption is large, and harsh conditions such as hydrothermal and the like are not used for synthesizing the mesoporous molecular sieve.
In addition, coal combustion produces waste fly ash, as well as power plant flue gas particles, nitrogen oxides, carbon oxides, sulfur dioxide, and the like. Nitrogen Oxides (NO)x) The pollution-free air purifying agent is one of main pollutants in the atmosphere, and the large amount of the pollution-free air purifying agent in the atmosphere can not only cause direct harm to the ecological environment and human health, but also react with other pollutants to form secondary pollution with larger harm. A series of emission standards such as thermal power plant atmospheric pollutant emission standard issued after 2011 aim at NO of fixed emission sources such as thermal power plants and industrial furnacesxEmissions have established more stringent emission standards. In the face of increasingly stringent emission standards, NOxResearch and development of control techniques has received much attention.
Selective Catalytic Reduction (SCR) process is relatively mature in technology and removes NOxHigh efficiency, and becomes the mainstream denitration technology of coal-fired power plants. At present, the vanadium-tungsten-titanium catalyst has better denitration efficiency and sulfur dioxide poisoning resistanceThe method is widely applied to removing nitrogen oxides discharged by fixed sources such as coal-fired thermal power plants, but has the defects of high denitration temperature, high denitration cost, easy loss of vanadium, secondary pollution caused by vanadium, high toxicity and the like; therefore, the development of an efficient, low-pollution and low-cost SCR denitration technology suitable for the national conditions of China is urgently needed.
The fly ash contains iron element, and if the iron element can be comprehensively utilized, the iron element is loaded on a molecular sieve, so that the preparation of the iron-based molecular sieve catalyst can reduce the cost of the catalyst and improve the comprehensive utilization rate of the fly ash.
Disclosure of Invention
The invention aims to improve the efficiency of a denitration catalyst and solve the problem of high-value utilization of fly ash, and provides a fly ash-based denitration catalyst, a preparation method thereof and a denitration method. The denitration catalyst contains alumina in the composition and has a micropore and mesopore double-pore structure in the structure, so that the denitration effect of the catalyst can be improved. In addition, the denitration catalyst can realize the utilization of the fly ash and reduce the pollution of the fly ash.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a method for preparing a fly ash-based denitration catalyst, the method comprising: (1) mixing and dissolving the fly ash and the acid liquor, and filtering to obtain iron-removing liquid and iron-removing fly ash; (2) carrying out alkali dissolution reaction on the deironing fly ash and alkali liquor, and filtering to obtain desiliconized solution; (3) mixing the desiliconized solution with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and adjusting the pH value to acidity to obtain a synthetic mother solution; (4) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain an SBA-15 mesoporous molecular sieve; (5) and (3) soaking the SBA-15 mesoporous molecular sieve by using a cobalt nitrate solution and the iron removal liquid, and performing rotary evaporation by using ethanol to obtain the denitration catalyst.
Preferably, in the step (1), the concentration of the acid solution is 1-3 mol/L, and the mass ratio of the fly ash to the acid solution is 100: (60-80), wherein the acid solution is hydrochloric acid or sulfuric acid.
Preferably, in the step (2), the mass ratio of the deironing fly ash to the alkali liquor is 100: (40-70): (100-200); the alkali liquor is sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the alkali dissolution reaction temperature is 80-100 ℃, and the alkali dissolution reaction time is 4-6 h.
Preferably, the deironing fly ash contains 40-45 g/L of SiO245-55 g/L of Al2O3。
Preferably, in the step (3), the pH is adjusted so that the pH of the synthesis mother liquor is 3 to 5.
Preferably, the SiO is added to 100 parts by weight of the synthesis mother liquor2The addition amount of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is 95-120 parts by weight.
Preferably, the desiliconization liquid contains 45-55 g/L SiO26 to 10g/L of Al2O33-4 mg/L Fe2O3。
Preferably, in the step (4), the temperature of the hydrothermal crystallization reaction is 100-120 ℃, the pressure of the hydrothermal crystallization reaction is 2-6 MPa, and the time of the hydrothermal crystallization is 48-72 hours.
Preferably, in the step (5), the concentration of the iron removing liquid in terms of Fe is 1-2 mol/L; the dosage of the iron removing liquid is 100-400 ml relative to 100g of the SBA-15 mesoporous molecular sieve; the concentration of the cobalt nitrate solution is 0.01-0.03 mol/L, and the dosage of the cobalt nitrate solution is 2000-10000 ml relative to 100g of the SBA-15 mesoporous molecular sieve.
In a second aspect of the present invention, there is provided a fly ash-based denitration catalyst prepared by the method of the present invention, wherein the denitration catalyst contains 5 to 8 wt% of Al based on the total weight of the denitration catalyst2O370 to 90% by weight of SiO25 to 20% by weight of Fe2O35 to 25% by weight of cobalt oxide.
Preferably, the denitration catalyst contains micropores and mesopores, and the volume of the micropores accounts for 10-20 vol% of the total pore volume of the denitration catalyst.
Preferably, the denitration catalyst has a mesoporous pore volumeIs 0.7 to 0.9cm3The volume of the micropores of the denitration catalyst is 0.2-0.4 cm3/g。
Preferably, the specific surface area of the denitration catalyst is 740-900 m2(ii)/g; the pore diameter of the denitration catalyst is 6-10 nm, and the average particle size of the denitration catalyst is 12-21 nm.
In a third aspect of the invention, a flue gas denitration method is provided, which comprises contacting industrial waste gas containing nitrogen oxides and mixed gas containing ammonia gas, oxygen and nitrogen with the denitration catalyst of the invention at a temperature of 200-300 ℃ to perform denitration reaction; in the industrial waste gas, the volume concentration of nitrogen oxides calculated by NO is 100-1000 ppm, the oxygen content in the mixture is 3-5 vol%, and the molar ratio of ammonia gas to the nitrogen oxides calculated by NO in the industrial waste gas is (1-3): 1; the volume airspeed of the total feeding amount of the industrial waste gas and the ammonia gas atmosphere is 3000-150000 h-1。
According to the technical scheme, the method adopts the fly ash as a raw material, and combines an alkali dissolution reaction and a hydrothermal crystallization reaction to prepare the mesoporous molecular sieve which contains Al and has a microporous and mesoporous double-pore structure SBA-15, and then the mesoporous molecular sieve is used as a carrier to load cobalt and iron recovered from the fly ash to obtain the denitration catalyst. Not only the fly ash is well utilized to generate high added value, but also the obtained SBA-15 mesoporous molecular sieve with the structural characteristics can provide better catalytic performance for a denitration catalyst in the flue gas denitration reaction, and especially NO in the waste can be enabled to be in the medium-low temperature conditionxThe concentration of the catalyst is reduced by 90-98%, and the denitration effect is improved.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of the fly ash-based denitration catalyst;
fig. 2 is a graph showing the denitration efficiency of the denitration catalysts prepared in examples 1 to 3 and comparative examples 2 to 3.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect of the present invention, there is provided a method for preparing a fly ash-based denitration catalyst, as shown in fig. 1, the method comprising:
(1) mixing and dissolving the fly ash and the acid liquor, and filtering to obtain iron-removing liquid and iron-removing fly ash;
(2) carrying out alkali dissolution reaction on the deironing fly ash and alkali liquor, and filtering to obtain desiliconized solution;
(3) mixing the desiliconized solution with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and adjusting the pH value to acidity to obtain a synthetic mother solution;
(4) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain an SBA-15 mesoporous molecular sieve;
(5) and (3) soaking the SBA-15 mesoporous molecular sieve by using a cobalt nitrate solution and the iron removal liquid, and performing rotary evaporation by using ethanol to obtain the denitration catalyst.
In the invention, fly ash is used as a raw material. The fly ash may be coal residue from a coal fired power plant and may generally comprise: 35 to 55% by weight of Al2O330 to 50% by weight of SiO20 to 0.5% by weight of SO30 to 0.3% by weight of K2O, 0 to 0.5 wt% CaO, 0 to 6 wt% TiO20 to 1% by weight of Fe2O30 to 1 wt% of MgO and 0 to 5 wt% of other substances.
According to the invention, step (1) can extract iron in the fly ash as an active component required in step (5). Preferably, in the step (1), the concentration of the acid solution is 1-3 mol/L, and the mass ratio of the fly ash to the acid solution is 100: (60-80), wherein the acid solution is hydrochloric acid or sulfuric acid.
According to the invention, the silicon and aluminum elements in the fly ash can be activated through alkali dissolution reaction by adding alkali in the step (2), and the fly ash is treated to obtain desilication solution suitable for synthesizing the SBA-15 mesoporous molecular sieve. The dosage of the deironing fly ash and the alkali liquor can meet the requirement of the alkali dissolution reaction. Preferably, in the step (2), the iron-removed fly ash: alkali: the mass ratio of water is 100: (40-70): (100-200).
According to the present invention, in the step (2), preferably, the alkali solution is a sodium hydroxide solution and/or a potassium hydroxide solution.
According to the invention, the conditions of the alkali-soluble reaction in the step (2) are satisfied to obtain the desiliconized solution suitable for synthesizing the SBA-15 mesoporous molecular sieve. Preferably, the alkali dissolution reaction temperature is 80-100 ℃, and the alkali dissolution reaction time is 4-6 h.
According to the invention, in the step (2), preferably, the deironing fly ash contains 40-45 g/L of SiO245-55 g/L of Al2O3。
In the step (2), the desiliconized solution is obtained and simultaneously a filter cake can be obtained, and the filter cake can be further used for extracting and producing alumina products. The invention can also utilize the fly ash to obtain the denitration catalyst and simultaneously provide the production of alumina products.
According to the invention, the step (3) is used for further preparing the synthesis mother liquor required by the hydrothermal crystallization reaction of the step (4). Preferably, in step (3), the pH adjustment is such that the pH of the synthesis mother liquor is not more than 5; preferably, the pH is 3 to 5. Preferably, the pH can be adjusted by adding hydrochloric acid, sulfuric acid or nitric acid with the concentration of 1-2 mol/L into the desilication solution.
In the present invention, the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123, PEO-PPO-PEO) in step (3) is used as a template for synthesizing the SBA-15 mesoporous molecular sieve, and is commercially available, such as P123 produced by BASF corporation, Germany. Preferably, the SiO is added to 100 parts by weight of the synthesis mother liquor2The addition amount of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is 95-120 parts by weight.
According to the invention, the mixing and preparing process in the step (3) can be adding the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer into the desilication solution after pH adjustment, and stirring at 35-40 ℃ for at least 10h, such as 10-20 h; obtaining the prepared synthetic mother liquor.
According to the invention, preferably, the desiliconization liquid contains 45-55 g/L SiO26 to 10g/L of Al2O33-4 mg/L Fe2O3。
According to the invention, the step (4) is carried out hydrothermal crystallization reaction, and the SBA-15 molecular sieve is prepared from the synthetic mother liquor obtained in the step (3). The hydrothermal crystallization reaction may be carried out by placing the synthesis mother liquor in a closed autoclave, for example, pouring into a stainless steel reaction kettle lined with polytetrafluoroethylene. Preferably, the temperature of the hydrothermal crystallization reaction is 100-120 ℃, the pressure of the hydrothermal crystallization reaction is 2-6 MPa, and the time of the hydrothermal crystallization is 48-72 h.
In the invention, after the hydrothermal crystallization reaction is finished, the obtained product can be sequentially filtered, washed, dried and calcined to obtain SBA-15 mesoporous molecular sieve powder. Wherein the washing step can be carried out by washing the colloid obtained by filtration with deionized water until the colloid is neutral. The drying can be carried out in an oven at 90-100 ℃ for 2-4 h. The calcination can be carried out at 500-600 ℃ for 4-8 h, wherein the heating rate can be 3-6 ℃/min.
In the method provided by the invention, the SBA-15 mesoporous molecular sieve prepared from the fly ash can be obtained through the steps. Compared with the conventional SBA-15 mesoporous molecular sieve, the SBA-15 mesoporous molecular sieve also contains Al in composition2O3And has two pore structures of micropore and mesopore. The composition of the SBA-15 mesoporous molecular sieve of the present invention can be determined by elemental analysis. Preferably, in the SBA-15 mesoporous molecular sieve of the invention, Al is contained2O3：SiO2The weight ratio of (A) may be 1: (5-7). In addition, the SBA-15 mesoporous molecular sieve also contains a small amount of other substances which come from fly ash and can be TiO2、CaO、Fe2O3、K2O, MgO or SO3But does not affect the performance of the SBA-15 mesoporous molecular sieve. The conventional SBA-15 mesoporous molecular sieve is synthesized by taking tetraethoxysilane as a raw materialIs formed of SiO2。
The SBA-15 mesoporous molecular sieve of the invention can analyze the crystal structure thereof by small-angle XRD. A strong characteristic diffraction peak appears near 0.8 DEG 2 theta in a small-angle XRD spectrogram, corresponds to a (100) crystal face of the molecular sieve SBA-15, two weaker characteristic diffraction peaks appear between 1.2 DEG and 2 DEG, respectively correspond to a (110) crystal face and a (200) crystal face of the molecular sieve SBA-15, and are characteristic diffraction peaks of a typical two-dimensional hexagonal channel structure, so that the molecular sieve is proved to be a mesoporous molecular sieve with typical framework characteristics of the SBA-15 molecular sieve, and the SBA-15 mesoporous molecular sieve has better crystallinity and order degree.
Furthermore, the SBA-15 mesoporous molecular sieve has a micropore and mesopore double-pore structure. The SBA-15 mesoporous molecular sieve warp N of the invention2Adsorption/desorption test to obtain N2And calculating an adsorption/desorption isothermal curve and BJH to obtain an aperture distribution diagram. From N2The adsorption/desorption isotherm curve shows that the molecular sieve has a typical type IV isotherm curve in IUPAC classification, which is a typical characteristic of mesoporous structures. The curve is at a relative pressure p/p0The obvious mutation is 0.4-0.8, and the phenomenon is caused by capillary condensation, and the hysteresis loop is H1 type. As can be seen from the pore size distribution diagram, the SBA-15 mesoporous molecular sieve has a highly ordered mesoporous structure, uniform pore size distribution and regular pore channels. Preferably, the mesoporous molecular sieve contains micropores, and the volume of the micropores accounts for 10-20 vol% of the total pore volume of the mesoporous molecular sieve. More preferably, the mesoporous molecular sieve has a mesoporous volume of 0.7-0.9 cm3The micropore volume of the mesoporous molecular sieve is 0.2-0.4 cm3(ii) in terms of/g. More preferably, the specific surface area of the mesoporous molecular sieve is 740-900 m2(ii) in terms of/g. According to the classification by IUPAC, pores with a pore size of less than 2nm are microporous and pores with a pore size between 2nm and 50nm are mesoporous.
The SBA-15 mesoporous molecular sieve can be further observed by a TEM (transmission electron microscope), and the pore array structure of the SBA-15 mesoporous molecular sieve is observed. The TEM image shows a hexagonal image and a striped image of the SBA-15 mesoporous molecular sieve of the present invention in the (100) direction, showing that the SBA-15 mesoporous molecular sieve of the present invention has a typical highly ordered two-dimensional hexagonal phase structure, and the mesoporous pore size and average particle size of the SBA-15 mesoporous molecular sieve of the present invention can be obtained from the TEM image. Preferably, the pore diameter of the mesoporous molecular sieve is 6-10 nm, and the average particle size of the mesoporous molecular sieve is 12-21 nm.
In the invention, the combination of alkali dissolution reaction and hydrothermal crystallization reaction is adopted to realize the preparation of the SBA-15 mesoporous molecular sieve with the composition and the structural characteristics from the fly ash.
According to the invention, the step (5) is used for introducing active components into the obtained SBA-15 mesoporous molecular sieve to prepare the denitration catalyst. According to the invention, active component cobalt can be introduced, and the iron removing liquid obtained in the step (1) is used as a raw material for introducing the active component, preferably, in the step (5), the concentration of the iron removing liquid calculated by Fe is 1-2 mol/L; the dosage of the iron removing liquid is 100-400 ml relative to 100g of the SBA-15 mesoporous molecular sieve; the concentration of the cobalt nitrate solution is 0.01-0.03 mol/L, and the dosage of the cobalt nitrate solution is 2000-10000 ml relative to 100g of the SBA-15 mesoporous molecular sieve. The method provided by the invention can fully utilize useful substances in the fly ash and improve the utilization value of the fly ash.
According to the invention, the product obtained by rotary evaporation of ethanol is calcined at 500-600 ℃ for 4-6 h to obtain the denitration catalyst of SBA-15 mesoporous molecular sieve loaded with Co and Fe.
In a second aspect of the present invention, there is provided a fly ash-based denitration catalyst prepared by the method of the present invention, wherein the denitration catalyst contains 5 to 8 wt% of Al based on the total weight of the denitration catalyst2O370 to 90% by weight of SiO25 to 20% by weight of Fe2O35 to 25% by weight of cobalt oxide.
The denitration catalyst is a coal ash-based denitration catalyst, is prepared by taking coal ash as a raw material, and also contains about 0.1-3 wt% of impurities, wherein the total content of all the components is 100 wt%.
The fly ash-based denitration catalyst provided by the invention is a denitration catalyst of SBA-15 mesoporous molecular sieve loaded with Co and Fe. The composition of the denitration catalyst can be determined by elemental analysis.
According to the classification by IUPAC, pores with a pore size of less than 2nm are microporous and pores with a pore size between 2nm and 50nm are mesoporous. Preferably, the denitration catalyst contains micropores and mesopores, and the volume of the micropores accounts for 10-20 vol% of the total pore volume of the denitration catalyst.
Preferably, the mesoporous volume of the denitration catalyst is 0.7-0.9 cm3The volume of the micropores of the denitration catalyst is 0.2-0.4 cm3/g。
Preferably, the specific surface area of the denitration catalyst is 740-900 m2(ii)/g; the pore diameter of the denitration catalyst is 6-10 nm, and the average particle size of the denitration catalyst is 12-21 nm.
In a third aspect of the invention, a flue gas denitration method is provided, which comprises contacting industrial waste gas containing nitrogen oxides and mixed gas containing ammonia gas, oxygen and nitrogen with the denitration catalyst of the invention at a temperature of 200-300 ℃ to perform denitration reaction; in the industrial waste gas, the volume concentration of nitrogen oxides calculated by NO is 100-1000 ppm, the oxygen content in the mixture is 3-5 vol%, and the molar ratio of ammonia gas to the nitrogen oxides calculated by NO in the industrial waste gas is (1-3): 1; the volume airspeed of the total feeding amount of the industrial waste gas and the ammonia gas atmosphere is 3000-150000 h-1。
The present invention will be described in detail below by way of examples.
In the following examples, the crystal structure of the molecular sieve produced was determined by small angle XRD analysis using D8ADVANCE from Bruker, Germany, with a test scan rate of 0.5 DEG/min to 5 DEG/min;
the pore structure of the prepared molecular sieve is determined by N2The adsorption method comprises using ASAP 2020 physical adsorption apparatus of Micromeritics, USA, and the adsorption medium is N2；
The mesoporous aperture and the average particle size of the prepared molecular sieve are measured by TEM, a JEM ARM200F spherical aberration correction transmission electron microscope of JEOL company is used, and a sample is placed on a copper net and observed after being subjected to ultrasonic dispersion in ethanol;
the composition of the molecular sieve obtained was measured by X-ray fluorescence elemental analysis using a ZSX PrimusX-ray fluorescence spectrometer from Rigaku corporation, Japan.
The fly ash used in the following examples was from Shenhua quasi-Geer energy Limited company and had the chemical composition shown in Table 1:
TABLE 1
Example 1
(1) Stirring 10g of fly ash and 100mL of 2mol/L hydrochloric acid at 80 ℃ for 2h to remove iron, carrying out suction filtration and washing, and drying a filter cake at 95 ℃ to obtain the iron-removed fly ash, wherein Fe in iron-removed liquid3+The content was 1.5 mol/L.
(2) Mixing the deironing fly ash, NaOH and water according to a mass ratio of 100: 48: 100, then carrying out alkali dissolution reaction for 4 hours at 100 ℃, then filtering the obtained product to obtain desiliconized solution, wherein the desiliconized solution contains 51.5g/L of SiO27.9g/L of Al2O33.4mg/L of Fe2O3；
(3) Adding 100ml of 2mol/L hydrochloric acid into 30ml of desiliconized solution, and adjusting the pH value of the desiliconized solution to 3; then adding 43g of P123 into 1L of desiliconized solution, and continuously stirring for 10h at 35 ℃ to prepare synthetic mother liquor;
(4) placing the synthetic mother liquor into a stainless steel reaction kettle (KH-100 ml autoclave of Nicotitaceae chemical equipment Co., Ltd.) with polytetrafluoroethylene lining, and performing hydrothermal crystallization reaction at 110 deg.C under 4MPa for 48 h; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6 hours to obtain molecular sieve powder;
and carrying out small-angle XRD (X-ray diffraction) test on the obtained molecular sieve powder, wherein an obtained spectrogram has a strong characteristic diffraction peak near 0.8 degrees at 2 theta, corresponds to a (100) crystal face of the molecular sieve SBA-15, has two weaker characteristic diffraction peaks between 1.2 and 2 degrees, respectively corresponds to a (110) crystal face and a (200) crystal face of the molecular sieve SBA-15, is a characteristic diffraction peak of a typical two-dimensional hexagonal pore channel structure, and shows that the molecular sieve has the material framework characteristics of the SBA-15 molecular sieve.
Subjecting the obtained molecular sieve powder to N2The pore structure data obtained from the adsorption/desorption tests are shown in table 2.
TEM observation of the obtained molecular sieve powder shows that the SBA-15 mesoporous molecular sieve of the invention has a typical highly ordered two-dimensional hexagonal phase structure, and the mesoporous pore diameter and the average particle size of the SBA-15 mesoporous molecular sieve can be obtained from a TEM image, and the results are shown in Table 2.
(5) Adding 4mL of 1.5mol/L iron removal liquid and 20mL of 0.02mol/L cobalt nitrate solution into 1g of SBA-15 mesoporous molecular sieve, magnetically stirring for 24 hours at 60 ℃, adding ethanol, stirring and evaporating to dryness to obtain the iron-based SBA-15 molecular sieve denitration catalyst.
The obtained denitration catalyst was subjected to composition measurement, and contained 5.9 wt% of Al2O383.8% by weight of SiO25% by weight of Fe2O35% by weight of cobalt oxide.
Subjecting the obtained denitration catalyst to N2The pore structure, mesoporous pore diameter and particle size data obtained by adsorption/desorption tests and TEM observation are shown in table 3.
Example 2
(1) Stirring 10g of fly ash and 100mL of 1mol/L sulfuric acid at 80 ℃ for 2h to remove iron, carrying out suction filtration and washing, and drying a filter cake at 95 ℃ to obtain the iron-removed fly ash, wherein Fe in iron-removed liquid3+The content was 1.2 mol/L.
(2) Mixing iron-removed fly ash, KOH and water according to the mass ratio of 100: 67: 100, then carrying out alkali dissolution reaction for 6h at the temperature of 80 ℃, then filtering the obtained product to obtain desiliconized solution containing 55g/L of SiO210g/L of Al2O33.0mg/L of Fe2O3；
(3) Adding 100ml of 2mol/L HNO into 30ml of desiliconized solution3Adjusting the pH value of the desiliconization solution to 5; then 53g of P123 is added into 1L of desiliconized solution, and the mixture is continuously stirred for 10 hours at the temperature of 35 ℃ to prepare synthetic mother liquor;
(4) putting the synthetic mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization reaction for 48 hours at 110 ℃ and 6 MPa; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
And carrying out small-angle XRD (X-ray diffraction) test on the obtained molecular sieve powder, and indicating that the molecular sieve has the material framework characteristics of the SBA-15 molecular sieve.
Subjecting the obtained molecular sieve powder to N2The pore structure data obtained from the adsorption/desorption tests are shown in table 2.
The molecular sieve powder obtained was subjected to TEM observation, and the results of the mesoporous pore diameter and the average particle size of the SBA-15 mesoporous molecular sieve are shown in table 2.
(5) Adding 5mL of 1.2mol/L iron removal liquid and 30mL of 0.03mol/L cobalt nitrate solution into 1g of SBA-15 mesoporous molecular sieve, magnetically stirring for 24 hours at 60 ℃, adding ethanol, stirring and evaporating to dryness to obtain the iron-based SBA-15 molecular sieve denitration catalyst.
The obtained denitration catalyst was subjected to composition measurement, and contained 6.2% by weight of Al2O377.4% by weight of SiO25% by weight of Fe2O311.3% by weight of cobalt oxide.
Subjecting the obtained denitration catalyst to N2The pore structure, mesoporous pore diameter and particle size data obtained by adsorption/desorption tests and TEM observation are shown in table 3.
Example 3
(1) Stirring 10g of fly ash and 100mL of 3mol/L hydrochloric acid at 80 ℃ for 2h to remove iron, carrying out suction filtration and washing, and drying a filter cake at 95 ℃ to obtain the iron-removed fly ash, wherein Fe in iron-removed liquid3+The content is 2 mol/L.
(2) Mixing the deironing fly ash, NaOH and water according to a mass ratio of 100: 70: 100, then carrying out alkali dissolution reaction for 5 hours at 95 ℃, then filtering the obtained product to obtain desiliconized solution, and analyzing and determining that the desiliconized solution contains 51.5g/L SiO27.9g/L of Al2O34.0mg/L of Fe2O3；
(3) 50ml of 2mol/L H was added to 30ml of the desiliconized solution2SO4Adjusting the pH value of the desiliconization solution to 3.5; then adding 49g of P123 into 1L of desiliconized solution, and continuously stirring for 10h at 35 ℃ to prepare synthetic mother liquor;
(4) putting the synthetic mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization reaction for 48 hours at 110 ℃ and 2 MPa; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
And carrying out small-angle XRD (X-ray diffraction) test on the obtained molecular sieve powder, and indicating that the molecular sieve has the material framework characteristics of the SBA-15 molecular sieve.
Subjecting the obtained molecular sieve powder to N2The pore structure data obtained from the adsorption/desorption tests are shown in table 2.
The molecular sieve powder obtained was subjected to TEM observation, and the results of the mesoporous pore diameter and the average particle size of the SBA-15 mesoporous molecular sieve are shown in table 2.
(5) Adding 3mL of 2mol/L iron removal liquid and 20mL of 0.02mol/L cobalt nitrate solution into 1g of SBA-15 mesoporous molecular sieve, magnetically stirring for 24 hours at 60 ℃, adding ethanol, stirring and evaporating to dryness to obtain the iron-based SBA-15 molecular sieve denitration catalyst.
The obtained denitration catalyst was subjected to composition measurement, and contained 8 wt% of Al2O379.3% by weight of SiO25% by weight of Fe2O35% by weight of cobalt oxide.
Subjecting the obtained denitration catalyst to N2The pore structure, mesoporous pore diameter and particle size data obtained by adsorption/desorption tests and TEM observation are shown in table 3.
Comparative example 1
(1) Mixing fly ash, NaOH and water according to a mass ratio of 100: 64: 200, then carrying out alkali dissolution reaction at 95 ℃ for 30min, then filtering the obtained product to obtain filtrate, and analyzing and determining that the filtrate contains 45g/L of SiO26g/L of Al2O3；
(2) Adding 43g of P123 into 1L of filtrate to obtain a mixed solution; adding 2mol/L HCl into the mixed solution to adjust the pH value to 10, synthetic colloid cannot be obtained, and the molecular sieve cannot be produced.
Comparative example 2
(1) Mixing fly ash, NaOH and water according to a mass ratio of 100: 64: 200, then carrying out alkali dissolution reaction at 95 ℃ for 30min, then filtering the obtained product to obtain filtrate, and analyzing and determining that the filtrate contains 45g/L of SiO26g/L of Al2O3；
(2) Adding 43g of P123 into 1L of filtrate to obtain a mixed solution; adding 2mol/L HCl into the mixed solution to adjust the pH value to 3, fully stirring at 35-40 ℃, standing and aging in a 95 ℃ oven for 24 hours, filtering, washing to be neutral, and drying at 95 ℃ for 3 hours; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
The molecular sieve powder obtained was analyzed and the results are shown in table 2.
(3) Adding 4mL of 1.5mol/L iron removal liquid and 20mL of 0.02mol/L cobalt nitrate solution into 1g of SBA-15 mesoporous molecular sieve, magnetically stirring for 24 hours at 60 ℃, adding ethanol, stirring and evaporating to dryness to obtain the iron-based SBA-15 molecular sieve denitration catalyst.
The obtained denitration catalyst was subjected to composition measurement, and contained 5.9 wt% of Al2O383.8% by weight of SiO25% by weight of Fe2O35% by weight of cobalt oxide.
Subjecting the obtained denitration catalyst to N2The pore structure, mesoporous pore diameter and particle size data obtained by adsorption/desorption tests and TEM observation are shown in table 3.
Comparative example 3
(1) Mixing fly ash and NaOH according to a mass ratio of 100: 64, then calcined at 550 ℃ for 2h, ground after cooling and mixed with water (fly ash: water mass ratio 100: 200). Because a large amount of hydrated SiO is formed in the water leaching process of adding the alkali sintering slag into the aluminum extraction residue by the acid method2Gel precipitation, no supernatant can be formed, and only suspension can be obtained;
(2) adding 2mol/L HCl into the suspension, and adjusting the pH value to 3; then adding 43g of P123 into 1L of filtrate, and continuously stirring for 10h at 35 ℃ to prepare synthetic mother liquor;
(3) putting the synthetic mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization reaction for 48 hours at 110 ℃ and 4 MPa; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
The molecular sieve powder obtained was analyzed and the results are shown in table 2.
(4) Adding 4mL of 1.5mol/L iron removal liquid and 20mL of 0.02mol/L cobalt nitrate solution into 1g of SBA-15 mesoporous molecular sieve, magnetically stirring for 24 hours at 60 ℃, adding ethanol, stirring and evaporating to dryness to obtain the iron-based SBA-15 molecular sieve denitration catalyst.
The obtained denitration catalyst was subjected to composition measurement, and contained 0% by weight of Al2O389.2% by weight of SiO25% by weight of Fe2O35% by weight of cobalt oxide.
Subjecting the obtained denitration catalyst to N2The pore structure, mesoporous pore diameter and particle size data obtained by adsorption/desorption tests and TEM observation are shown in table 3.
Example 4
The denitration catalysts prepared in examples 1 to 3 and comparative examples 2 to 3 were subjected to a flue gas denitration reaction, respectively.
0.2g of the denitration catalyst is respectively filled in a fixed tubular reactor, and simulated flue gas (300ppm NO, 300ppm NH) is introduced33.0% by volume of O2，N2As balance gas), the volume space velocity is 120000h-1And measuring the denitration efficiency of the catalyst in the process of increasing the temperature from 100 ℃ to 500 ℃, wherein the denitration efficiency is calculated by the following method:
αNO＝[(Cin-Cout)/Cin]×100％
Cinrepresents the volume concentration of NO in the introduced flue gas, ppm;
Coutdenotes the reactor outletVolume concentration of NO in the gas, ppm.
Fig. 2 shows denitration efficiency versus temperature curves measured by performing the above-described denitration reactions for the prepared denitration catalysts of examples 1 to 3 and comparative examples 2 to 3, respectively.
TABLE 2
| Numbering | Example 1 | Example 2 | Example 3 | Comparative example 2 | Comparative example 3 |
| Al2O3To weight percent | 6.5 | 7.4 | 8.3 | 6.5 | —— |
| SiO2To weight percent | 93.5 | 92.6 | 91.7 | 93.5 | 100 |
| Specific surface area, m2/g | 749 | 894 | 796 | 694 | 632 |
| Total pore volume, cm3/g | 0.84 | 0.94 | 0.86 | 0.79 | 0.78 |
| Pore volume of micropores, cm3/g | 0.32 | 0.29 | 0.25 | —— | 0.21 |
| Pore volume of mesoporous, cm3/g | 0.75 | 0.85 | 0.80 | 0.86 | 0.71 |
| The volume of the micropores accounts for the ratio, v% | 12 | 15 | 18 | —— | 10 |
| Pore size, nm | 6.9 | 7.1 | 8.4 | 7.3 | 8.0 |
| Particle size, nm | 12.16 | 21 | 17.9 | 22.5 | 23 |
TABLE 3
| Numbering | Example 1 | Example 2 | Example 3 | Comparative example 2 | Comparative example 3 |
| Al2O3To weight percent | 5.9 | 6.2 | 8 | 5.9 | —— |
| SiO2To weight percent | 83.8 | 77.4 | 79.3 | 83.8 | 89.2 |
| Fe2O3To weight percent | 5.0 | 5 | 5 | 5 | 5 |
| Cobalt oxide,% by weight | 5.0 | 11.3 | 5 | 5 | 5 |
| Specific surface area, m2/g | 703 | 852 | 724 | 628 | 602 |
| Total pore volume, cm3/g | 0.74 | 0.84 | 0.78 | 0.76 | 0.68 |
| Pore volume of micropores, cm3/g | 0.19 | 0.21 | 0.20 | —— | 0.11 |
| Pore volume of mesoporous, cm3/g | 0.53 | 0.79 | 0.72 | 0.80 | 0.61 |
| The volume of the micropores accounts for the ratio, v% | 12 | 11 | 14 | —— | 8.5 |
| Pore size, nm | 6.63 | 6.8 | 7.5 | 6.3 | 6.9 |
| Particle size, nm | 16.46 | 17.45 | 18.42 | 19.34 | 17.52 |
As can be seen from the examples and the data in Table 2, the present invention can realize the synthesis of SBA-15 mesoporous molecular sieve by using fly ash, wherein the SBA-15 mesoporous molecular sieve contains alumina and has a mesoporous and microporous dual-pore structure in the pore structure. As can be seen from the curve of FIG. 2, the denitration efficiency of the catalyst of the embodiment of the invention is higher than that of the comparative catalyst, and the denitration efficiency at the medium and low temperature is much higher than that of the comparative catalyst, so that NO in the gas can be realized in the medium and low temperature range of 150 ℃ to 300 DEG CxThe concentration of the catalyst is reduced by more than 90%, and the catalyst has better denitration activity.
As can be seen from the preparation processes shown in the examples, the method for preparing the SBA-15 mesoporous molecular sieve from the fly ash provided by the invention comprises the steps of firstly treating the fly ash by an alkali dissolution reaction to obtain a filtrate suitable for synthesis of the mesoporous molecular sieve, then adjusting and preparing the filtrate into a synthesis mother solution, finally obtaining the SBA-15 mesoporous molecular sieve by a hydrothermal crystallization method, and combining the alkali dissolution reaction and the hydrothermal crystallization reaction to obtain the SBA-15 mesoporous molecular sieve with the composition characteristics and the double-pore structure.
In comparative example 1, the mesoporous molecular sieve could not be synthesized by using an alkali-soluble reaction in combination with the prior art to adjust the filtrate to be alkaline, rather than by hydrothermal crystallization.
In comparative example 2, the filtrate was adjusted to be acidic using an alkali-soluble reaction in combination with the prior art, but was aged by standing at 95 ℃ and the synthesized mesoporous molecular sieve had no micropores and did not have the double-pore structure of the SBA-15 mesoporous molecular sieve of the present invention.
In comparative example 3, the composition of the mesoporous molecular sieve obtained by using the alkali fusion reaction in combination with the hydrothermal crystallization reaction did not contain alumina, and the SBA-15 mesoporous molecular sieve having a composite pore structure and containing alumina could not be obtained.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method of preparing a fly ash-based denitration catalyst, the method comprising:
(1) mixing and dissolving the fly ash and the acid liquor, and filtering to obtain iron-removing liquid and iron-removing fly ash;
(2) carrying out alkali dissolution reaction on the deironing fly ash and alkali liquor, and filtering to obtain desiliconized solution;
(3) mixing the desiliconized solution with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and adjusting the pH value to acidity to obtain a synthetic mother solution; relative to 100 weight parts of SiO in the synthesis mother liquor2The addition amount of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is 95-120 parts by weight;
(4) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain an SBA-15 mesoporous molecular sieve; wherein, the SBA-15 mesoporous molecular sieve has two pore structures of micropore and mesopore;
(5) and (3) soaking the SBA-15 mesoporous molecular sieve by using a cobalt nitrate solution and the iron removal liquid, and performing rotary evaporation by using ethanol to obtain the denitration catalyst.
2. The method according to claim 1, wherein in the step (1), the concentration of the acid liquor is 1-3 mol/L, and the mass ratio of the fly ash to the acid liquor is 100: (60-80), wherein the acid solution is hydrochloric acid or sulfuric acid.
3. The method of claim 1, wherein, in step (2), the iron-removed fly ash: alkali: the mass ratio of water is 100: (40-70): (100-200); the alkali liquor is a sodium hydroxide solution and/or a potassium hydroxide solution;
preferably, the alkali dissolution reaction temperature is 80-100 ℃, and the alkali dissolution reaction time is 4-6 h;
preferably, the deironing fly ash contains 40-45 g/L of SiO245-55 g/L of Al2O3。
4. The process according to claim 1 or 2, wherein, in step (3), the pH adjustment is such that the synthesis mother liquor has a pH = 3-5; preferably, the desiliconization liquid contains 45-55 g/L SiO26 to 10g/L of Al2O33-4 mg/L Fe2O3。
5. The method according to claim 1, wherein in the step (4), the temperature of the hydrothermal crystallization reaction is 100 to 120 ℃, the pressure of the hydrothermal crystallization reaction is 2 to 6MPa, and the time of the hydrothermal crystallization is 48 to 72 hours.
6. The method according to claim 1, wherein in the step (5), the concentration of the iron-removing liquid in terms of Fe is 1-2 mol/L, and the iron-removing liquid is used in an amount of 100-400 mL relative to 100g of the SBA-15 mesoporous molecular sieve; the concentration of the cobalt nitrate solution is 0.01-0.03 mol/L, and the dosage of the cobalt nitrate solution is 2000-10000 mL relative to 100g of the SBA-15 mesoporous molecular sieve.
7. The fly ash-based denitration catalyst prepared by the method of any one of claims 1 to 6, wherein the denitration catalyst contains 5 to 8 wt% of Al based on the total weight of the denitration catalyst2O370 to 90% by weight of SiO25 to 20% by weight of Fe2O35 to 25% by weight of cobalt oxide; wherein said Al is2O3、SiO2、Fe2O3And cobalt oxide in a total amount of 100%.
8. The denitration catalyst according to claim 7, wherein the denitration catalyst contains micropores and mesopores, and a micropore volume accounts for 10 to 20 vol% of a total pore volume of the denitration catalyst.
9. The denitration catalyst of claim 8, wherein the denitration catalystThe mesoporous volume of the denitration catalyst is 0.7-0.9 cm3The volume of the micropores of the denitration catalyst is 0.2-0.4 cm3/g。
10. The denitration catalyst according to any one of claims 7 to 9, wherein the denitration catalyst has a specific surface area of 740 to 900m2(ii)/g; the pore diameter of the denitration catalyst is 6-10 nm, and the average particle size of the denitration catalyst is 12-21 nm.
11. A flue gas denitration method comprises the steps of contacting industrial waste gas containing nitrogen oxides and mixed gas containing ammonia gas, oxygen and nitrogen with the denitration catalyst of any one of claims 7 to 10 at the temperature of 200-300 ℃ to carry out denitration reaction; in the industrial waste gas, the volume concentration of nitrogen oxides calculated by NO is 100-1000 ppm, the oxygen content in the mixture is 3-5 vol%, and the molar ratio of ammonia gas to the nitrogen oxides calculated by NO in the industrial waste gas is (1-3): 1; the volume airspeed of the total feeding amount of the industrial waste gas and the ammonia gas atmosphere is 3000-150000 h-1。
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