CN111992223A - Catalyst for purifying flue gas of gas-fired boiler and preparation method thereof - Google Patents
Catalyst for purifying flue gas of gas-fired boiler and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003546 flue gas Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 44
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000005520 cutting process Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 229910052684 Cerium Inorganic materials 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- 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
- B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
- B01D53/8646—Simultaneous elimination of the components
- B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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Abstract
The invention belongs to the field of atmospheric pollutant treatment, and particularly relates to a catalyst for gas boiler flue gas purification and a preparation method thereof. The catalyst comprises the following raw materials in parts by weight: 2-8 parts of ferric nitrate and 0-5 parts of WO30.1-6 parts of MnO20.1-1.5 parts of Ir, 0-1.5 parts of Cu, 0.1-1 parts of Mn, 0.1-1 parts of Fe and 0-8 parts of SiO20-10 parts of Al2O350-60 parts of TiO2(ii) a The ferric nitrate and the nitric acidThe molar ratio of cerium is 2: 1; the MnO2The weight ratio of Mn to Mn is 6: 1; the urea is also included, and the molar ratio of the added amount to the ferric nitrate and the cerous nitrate is 5: 1; the Al is2O3Is a porous material. In the preparation process of the catalyst, Fe is generated in a solution of metal oxide and metalxCeyOzThe metal oxide and the metal are used as a catalyst and a dispersing agent at the same time, and Fe with small particle size is preparedxCeyOzThereby obtaining good low-temperature catalytic activity; and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of atmospheric pollutant treatment, and particularly relates to a catalyst for gas boiler flue gas purification and a preparation method thereof.
Background
With the economic development and the adjustment of energy structures in China, it is a necessary development trend to vigorously develop gas boilers to replace coal-fired boilers. Gas-fired boilers, however, often produce large amounts of CO during operation due to inadequate combustion, and in addition, produce large amounts of NOx pollutants during combustion.
Wherein CO is a common toxic and harmful gas and has strong toxicity to blood and nervous system. NOx is the major atmospheric pollutant, which is the primary precursor for greenhouse effect, acid rain, ozone depletion, photochemical smog, and haze. If the direct emission of CO and NOx can have negative effects on human health and the atmospheric environment.
The Selective Catalytic Reduction (SCR) denitration principle is that under the action of a catalyst at a certain temperature (300-400 ℃), a reducing agent selectively reduces NOX in flue gas into nontoxic and pollution-free N2And H2And O, the reducing agent for industrial application is mainly liquid ammonia, urea, ammonia water and the like. Currently, technologies which can be used for a gas boiler mainly include ammonia selective catalytic reduction (NH 3-SCR) and hydrocarbon selective catalytic reduction (HC-SCR) technologies. Although the NH3-SCR catalyst has high catalytic efficiency, the NH3-SCR catalyst has the defects of complex application equipment system, high construction and operation cost and low safety. The HC-SCR catalyst has low cost, but has the defects of low catalytic efficiency, easy generation of secondary pollution, narrow active temperature range and the like. However, carbon monoxide selective catalytic reduction (CO-SCR) catalysts have catalysisThe method has the advantages of high efficiency, no need of an additional reducing agent, good safety and the like, and is gradually a hotspot of research on denitration technology.
Elemental iridium (Ir) is considered to be a relatively active component for CO-SCR reactions, and Hideeki Hamada et al, Japan, studied Ir supported on SiO2The catalyst activity is higher, the ideal catalytic efficiency can be obtained under a larger space velocity, and Ba is added2+And WO3These elements can enhance the activity, but the cost is increased greatly. CeO supported by CuO was studied in Dong, a university of Nanjing, etc2The catalytic activity of the catalyst can reach more than 70 percent of efficiency, but the activity temperature is narrow.
Disclosure of Invention
Aiming at the technical problems, the invention provides a catalyst for purifying the flue gas of a gas-fired boiler, and the catalyst with good catalytic activity and low reaction temperature is obtained by compounding metal oxide and metal. Meanwhile, the preparation method of the catalyst is also provided, and the method is simple, easy to operate and suitable for industrialization.
The technical scheme of the invention is as follows:
a catalyst for purifying flue gas of a gas boiler comprises the following raw materials in parts by weight: 2-8 parts of ferric nitrate and 0-5 parts of WO30.1-6 parts of MnO20.1-1.5 parts of Ir, 0-1.5 parts of Cu, 0.1-1 parts of Mn, 0.1-1 parts of Fe and 0-8 parts of SiO20-10 parts of Al2O350-60 parts of TiO2(ii) a The molar ratio of the ferric nitrate to the cerium nitrate is 2: 1; the MnO2The weight ratio of Mn to Mn is 6: 1;
the urea is also included, and the molar ratio of the added amount to the ferric nitrate and the cerous nitrate is 5: 1;
the Al is2O3Is a porous material.
The preparation method of the catalyst comprises the following steps:
(1) preparing ferric nitrate and cerous nitrate aqueous solution, adding Ir, Cu, Mn, Fe and SiO2、Al2O3、TiO2Stirring uniformly;
(2) adding urea, and heating for reaction;
（3）filtering, adding WO3、MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying and then calcining at high temperature;
(5) cutting; are mounted as a module.
Preferably, the molar concentration of the ferric nitrate and cerous nitrate aqueous solution in the step (1) is 0.1-0.5 mol/L.
The catalyst prepared by the preparation method is applied to the purification of the flue gas of the gas-fired boiler.
The temperature of the application is 140-200 ℃, the CO purification rate is more than 90%, and the NOx purification rate is more than 90%.
Iron oxide and cerium oxide are used as active metal oxides to provide active oxygen for the purification process, and are matched with metal Ir, Cu, Mn and Fe in a certain proportion to promote NOx purification to obtain N2(ii) a In addition, the urea is calcined after being subjected to high-temperature reaction without being washed, so that the effect of protecting metal Ir and preventing the metal Ir from being agglomerated is achieved; compound oxide Fe generated at the same timexCeyOzStable structure, adsorption on porous Al2O3、TiO2、SiO2Inside, metallic Ir is further stabilized.
The invention has the beneficial effects that:
1. the preparation process is simple
Formation of Fe in solutions of metal oxides or metalsxCeyOzThe metal oxide and the metal are used as a catalyst and a dispersing agent at the same time, and Fe with small particle size is preparedxCeyOzThereby obtaining good low-temperature catalytic activity; and is suitable for industrial production.
2. Low purification temperature
The temperature of the catalyst at the present stage is above 200 ℃ when the purification effect is above 90%, and the temperature can be as low as 120 ℃ by adopting the scheme of the invention.
Drawings
FIG. 1 is a flow diagram of a honeycomb catalyst manufacturing process.
Detailed Description
Example 1
A preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 217.06g of cerium nitrate were dissolved in 15L of an aqueous solution, and 45.35 g of Ir, 30.23g of Mn, 30.23g of Fe and 1814g of TiO were added2、241.86 g SiO2Stirring uniformly;
(2) adding 450.45g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtering, adding 181.4 gMnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
The molar concentration of the ferric nitrate and cerous nitrate aqueous solution in the step (1) is 0.1-0.8 mol/L.
Example 2
A preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 217.06g of cerous nitrate were dissolved in 3L of an aqueous solution, and 12.10 g of Ir, 2.01 g of Mn, 12.10 g of Fe, 181.40 g of Cu and 6046.5 g of TiO were added2Stirring uniformly;
(2) adding 450.45g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtered and 604.65 g of WO are added3、12.10 g MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
Example 3
A preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 217.06g of cerium nitrate were dissolved in 6L of an aqueous solution, and 48.37 g of Ir, 24.19 g of Mn, 24.19 g of Fe, 48.37 g of Cu and 483.72 g of Al were added2O3、2660.46 g TiO2Stirring uniformly; the Al is2O3Is a porous material;
(2) adding 450.45g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtered and 604.65 g of WO are added3、145.14 g MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
MnO as compared with example 3 in comparative example 12The weight ratio of Mn to Mn is 5: 1;
a preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 217.06g of cerium nitrate were dissolved in 6L of an aqueous solution, and 48.37 g of Ir, 24.19 g of Mn, 24.19 g of Fe, 48.37 g of Cu and 483.72 g of Al were added2O3、2660.46 g TiO2Stirring uniformly; the Al is2O3Is a porous material;
(2) adding 450.45g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtered and 604.65 g of WO are added3、120.95 g MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
MnO as compared with example 3 in comparative example 22The weight ratio of Mn to Mn is 7: 1;
a preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 217.06g of cerium nitrate were dissolved in 6L of an aqueous solution, and 48.37 g of Ir, 24.19 g of Mn, 24.19 g of Fe, 48.37 g of Cu and 483.72 g of Al were added2O3、2660.46 g TiO2Stirring uniformly; the Al is2O3Is a porous material;
(2) adding 450.45g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtered and 604.65 g of WO are added3、169.33 g MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
Comparative example 3 molar ratio of iron nitrate to cerium nitrate was 3:1
A preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 143.26 g of cerium nitrate were dissolved in 5.32L of an aqueous solution, and 48.37 g of Ir, 24.19 g of Mn, 24.19 g of Fe, 48.37 g of Cu and 483.72 g of Al were added2O3、2660.46 g TiO2Stirring uniformly; the Al is2O3Is a porous material;
(2) adding 399.40 g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtered and 604.65 g of WO are added3、145.14 g MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
Comparative example 4 molar ratio of iron nitrate to cerium nitrate 1:1
A preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 434.12 g of cerous nitrate were dissolved in 8L of an aqueous solution, and 48.37 g of Ir, 24.19 g of Mn, 24.19 g of Fe, 48.37 g of Cu, and 483.72 g of Al were added2O3、2660.46 g TiO2Stirring uniformly; the Al is2O3Is a porous material;
(2) adding 600.6 g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtered and 604.65 g of WO are added3、120.95 g MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
Comparative example 5 differs from example 3 in the process
A preparation method of a catalyst for purifying flue gas of a gas-fired boiler comprises the following steps:
(1) 241.86 g of ferric nitrate and 217.06g of cerium nitrate were dissolved in 6L of an aqueous solution, and 48.37 g of Ir, 24.19 g of Mn, 24.19 g of Fe, 48.37 g of Cu and 604.65 g of WO were added3、145.14 g MnO2、483.72 g Al2O3、2660.46 g TiO2Stirring uniformly; the Al is2O3Is a porous material;
(2) adding 450.45g of urea, heating to 130 ℃, and reacting for 2 h;
(3) filtering, pressing and extruding and molding the honeycomb monomer;
(4) drying at 100 ℃, and then calcining at 200 ℃;
(5) cutting; are mounted as a module.
The embodiment has the following effects:
firstly, the catalysts prepared in examples 1-3 and comparative examples 1-5 are installed in a flue gas discharge port of a gas boiler, the temperature is about 115 ℃, an online sampling measuring device is installed, air is blown in from an inlet by a blower, the gas composition before flue gas of the gas boiler enters the catalyst is measured, the gas composition of the catalyst is discharged, the experimental conditions are kept the same during the test, and the specific results are shown in table 1.
TABLE 1 comparison of catalytic Effect of catalysts prepared in examples 1 to 3 and comparative examples 1 to 5
| Item | CO inlet volume fraction/% | NO entry volume fraction/% | O2Inlet volume fraction/% | H2O inlet volume fraction/% | CO oxidation rate/%) | Denitration rate/%) |
| Example 1 | 0.02 | 0.01 | 10.0 | 12.0 | 84 | 87 |
| Example 2 | 0.04 | 0.02 | 12.0 | 15.0 | 75 | 80 |
| Example 3 | 0.03 | 0.02 | 10.0 | 15.0 | 82 | 87 |
| Comparative example 1 | 0.03 | 0.02 | 10.0 | 15.0 | 52 | 56 |
| Comparative example 2 | 0.03 | 0.02 | 10.0 | 15.0 | 59 | 61 |
| Comparative example 3 | 0.03 | 0.02 | 10.0 | 15.0 | 38 | 41 |
| Comparative example 4 | 0.03 | 0.02 | 10.0 | 15.0 | 52 | 57 |
| Comparative example 5 | 0.03 | 0.02 | 10.0 | 15.0 | 54 | 59 |
Secondly, the composition of the flue gas (CO volume fraction 0.03%; NO volume fraction 0.02%) of the gas-fired boiler was simulated in the laboratory, and the catalytic effects of the catalysts prepared in examples 1 to 3 and comparative examples 1 to 5 were examined at different temperatures and different oxygen concentrations, and the results are shown in Table 2.
TABLE 2 catalytic Effect of the catalysts prepared in examples 1-3 and comparative examples 1-5 under laboratory conditions
| Item | Temperature of | O2Volume fraction | H2Volume fraction of O | Rate of CO oxidation | Denitration rate |
| Example 1 | 120℃ | 10.0% | 15.0% | 85% | 89% |
| Example 2 | 120℃ | 10.0% | 15.0% | 78% | 81% |
| Example 3 | 120℃ | 10.0% | 15.0% | 89% | 90% |
| Example 3 | 140℃ | 10.0% | 15.0% | 91% | 93% |
| Example 3 | 150℃ | 10.0% | 15.0% | 93% | 96% |
| Example 3 | 160℃ | 10.0% | 15.0% | 97% | 98% |
| Comparative example 1 | 150℃ | 10.0% | 15.0% | 64% | 69% |
| Comparative example 2 | 150℃ | 10.0% | 15.0% | 70% | 74% |
| Comparative example 3 | 150℃ | 10.0% | 15.0% | 53% | 54% |
| Comparative example 4 | 150℃ | 10.0% | 15.0% | 65% | 69% |
| Comparative example 5 | 150℃ | 10.0% | 15.0% | 68% | 72% |
Third, investigation of catalyst stability
The catalysts prepared in examples 1 to 3 and comparative examples 1 to 5 were installed in flue gas of a gas boiler (CO volume fraction 0.03%; NO volume fraction 0.02%; O)210% by volume; the temperature was about 115 ℃ C. for different times at the discharge outlet, the catalytic effect of the catalyst (based on the CO conversion) was examined. The results are shown in Table 3.
TABLE 3 stability test results of catalysts prepared in examples 1-3 and comparative examples 1-5
| Item | 3 months old | 6 months old | 9 months old | 12 months old | 15 months old |
| Example 1 | 76% | 73% | 70% | 65% | 60% |
| Example 2 | 71% | 68% | 64% | 58% | 51% |
| Example 3 | 79% | 78% | 75% | 72% | 68% |
| Comparative example 1 | 47% | 45% | 41% | 37% | 35% |
| Comparative example 2 | 52% | 49% | 46% | 42% | 38% |
| Comparative example 3 | 36% | 33% | 29% | 28% | 26% |
| Comparative example 4 | 49% | 46% | 42% | 39% | 36% |
| Comparative example 5 | 51% | 48% | 44% | 40% | 38% |
After the catalytic reaction for 15 months, taking down the catalyst, cutting one end, preparing a sample, and observing under a scanning electron microscope, the catalysts are all found to have agglomeration of different degrees, wherein the agglomeration degree of example 3 is the lightest, and the agglomeration of comparative example 3 is the most serious.
Claims (5)
1. A catalyst for purifying flue gas of a gas boiler is characterized by comprising the following raw materials in parts by weight: 2-8 parts of ferric nitrate and 0-5 parts of WO30.1-6 parts of MnO20.1-1.5 parts of Ir, 0-1.5 parts of Cu, 0.1-1 parts of Mn, 0.1-1 parts of Fe and 0-8 parts of SiO20-10 parts of Al2O350-60 parts of TiO2(ii) a The molar ratio of the ferric nitrate to the cerium nitrate is 2: 1; the MnO2The weight ratio of Mn to Mn is 6: 1;
the urea is also included, and the molar ratio of the added amount to the ferric nitrate and the cerous nitrate is 5: 1;
the Al is2O3Is a porous material.
2. A method for preparing the catalyst of claim 1, comprising the steps of:
(1) preparing ferric nitrate and cerous nitrate aqueous solution, adding Ir, Cu, Mn, Fe and SiO2、Al2O3、TiO2Stirring uniformly;
(2) adding urea, and heating for reaction;
(3) filtering, adding WO3、MnO2Pressing, and extruding and molding the honeycomb monomer;
(4) drying and then calcining at high temperature;
(5) cutting; are mounted as a module.
3. The method according to claim 2, wherein the molar concentration of the ferric nitrate and cerous nitrate aqueous solution in step (1) is 0.1-0.5 mol/L.
4. Use of the catalyst prepared by the preparation method of claim 2 for the purification of flue gas from a gas-fired boiler.
5. The use according to claim 4, wherein the temperature is 140 ℃ and 200 ℃, the CO purification rate is above 90%, and the NOx purification rate is above 90%.
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