CN111744490A - Iron-based denitration catalyst and preparation method thereof - Google Patents
Iron-based denitration catalyst and preparation method thereof Download PDFInfo
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- CN111744490A CN111744490A CN201910242497.0A CN201910242497A CN111744490A CN 111744490 A CN111744490 A CN 111744490A CN 201910242497 A CN201910242497 A CN 201910242497A CN 111744490 A CN111744490 A CN 111744490A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 24
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000011068 loading method Methods 0.000 claims abstract description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005751 Copper oxide Substances 0.000 claims abstract description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 claims description 10
- 229960004830 cetylpyridinium Drugs 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000007738 vacuum evaporation Methods 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- DJIOGHZNVKFYHH-UHFFFAOYSA-N 2-hexadecylpyridine Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=N1 DJIOGHZNVKFYHH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910003286 Ni-Mn Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J35/61—Surface area
- B01J35/615—100-500 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention provides an iron-based denitration catalyst, which comprises a carrier and a substrate, wherein the carrier comprises zirconium oxide and cerium oxide, the substrate comprises iron oxide and copper oxide, the mass ratio of the zirconium oxide to the cerium oxide is 1:0.6-1:0.8, the loading amount of iron is 5-7% by mass, the loading amount of copper is 7.5-22% by mass, and the mass ratio of the iron loading amount to the copper loading amount is 1:2.5-1: 4. The catalyst prepared by the method has ideal specific surface area, pore volume and pore diameter and shows ideal catalytic effect by controlling proper component proportion and reaction conditions.
Description
Technical Field
The invention relates to a denitration catalyst and a preparation method thereof, in particular to an iron-based denitration catalyst and a preparation method thereof.
Background
The nitrogen oxide is used as a main pollutant of the atmosphere, can directly stimulate the respiratory system of human beings and cause related diseases, and can form environmental problems such as acid rain, photochemical smog, ozone cavities, greenhouse effect and the like, thereby seriously affecting the safety and health of the human beings. Therefore, the work of treating and eliminating nitrogen oxides in the atmosphere is urgent.
The denitration technology mainly comprises two main types of combustion and flue gas treatment, wherein the former adopts the mode of changing combustion conditions and controlling the formation of nitrogen oxides by equipment, and the latter removes the nitrogen oxides in the flue gas by a physical-chemical method, and the main technology at present comprises the following steps: liquid absorption treatment, direct catalytic decomposition, low-temperature plasma decomposition, selective non-catalytic reduction, selective catalytic reduction and the like. Among them, the selective catalytic reduction technology has become the most important denitration means at present due to its advantages of high efficiency, good selectivity, high removal rate, etc.
The Chinese patent application with publication number CN109364968A discloses a low-temperature denitration catalyst and a preparation method, a mold and a preparation method thereof. The low-temperature denitration catalyst at least comprises: a catalyst support; the active catalytic auxiliary agent is attached to the catalyst carrier; the active catalytic promoter consists of transition metal oxides; and a first co-agent and a second co-agent attached to the catalyst support; the first coagent is comprised of a metal oxide; the second coagent is comprised of a metal oxide and a non-metal oxide. However, since the catalyst is prepared by a common mixing method, parameters such as specific surface area, pore volume, pore diameter and the like of the finally obtained catalyst are greatly limited, thereby causing poor catalytic performance.
The Chinese patent application with publication number CN109364943A discloses a Ni-Mn-based composite oxide catalyst, and the preparation method comprises the following steps: 1) dropwise adding a precipitant aqueous solution into a mixed aqueous solution of nickel acetate and manganese acetate, adjusting the pH of the mixed solution to 5-7, stirring for reaction for 1-1.5 h, aging for 4-5h, filtering, taking a precipitate, and washing the precipitate with deionized water and ethanol respectively until the pH is 7; 2) drying the precipitate washed in the step 1) at the temperature of 80 ℃ to obtain Ni-Mn mixture powder; 3) grinding the Ni-Mn mixture powder obtained in the step 2), and roasting in a muffle furnace in an air environment to obtain the Ni-Mn composite oxide catalyst. Similarly, due to the common mixed sintering process, parameters such as specific surface area, pore volume, pore diameter and the like of the finally obtained catalyst are greatly limited, so that the catalytic performance is poor.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an iron-based denitration catalyst and a preparation method thereof, aiming at achieving ideal catalytic effect and sulfur resistance.
It is an object of the present invention to provide an iron baseThe denitration catalyst comprises a carrier and a substrate, wherein the carrier comprises zirconium oxide and cerium oxide, the substrate comprises iron oxide and copper oxide, the mass ratio of the zirconium oxide to the cerium oxide is 1:0.6-1:0.8, the loading amount of iron is 5-7% by mass, the loading amount of copper is 7.5-22% by mass, the mass ratio of the iron loading amount to the copper loading amount is 1:2.5-1:4, and the specific surface area of the catalyst is 267-308m2The pore volume of the catalyst is 0.42-0.48cm2The pore diameter of the catalyst is 16.44-18.28 nm.
Further, the zirconium oxide is zirconium dioxide, and the cerium oxide is cerium oxide.
Further, the mass ratio of the zirconium oxide to the cerium oxide is 1: 0.78.
Further, the loading amount of the iron is 5% (mass fraction), and the loading amount of the copper is 16.5% (mass fraction).
Further, the specific surface area of the catalyst is 308m2The pore volume of the catalyst is 0.48cm2The pore diameter of the catalyst is 16.44 nm.
The second object of the present invention is to provide a method for preparing the iron-based denitration catalyst, which comprises the following steps:
1) preparing the raw materials according to the components and the content, wherein the zirconium source and the cerium source are respectively nano zirconium oxide and nano cerium oxide, and the iron source and the copper source are respectively soluble iron salt and soluble copper salt;
2) adding the nano zirconia and the nano cerium oxide with the contents into a deionized water solution, slowly dropwise adding an alkaline solution to adjust the pH of the solution to 9-11, heating to 55-75 ℃, adding cetylpyridine, carrying out constant temperature ultrasonic stirring for a certain time, then respectively adding PEG-600, soluble ferric salt and soluble copper salt, and continuously keeping constant temperature ultrasonic stirring at 55-75 ℃ in the period;
3) and (3) drying the solution by vacuum evaporation, washing, drying and calcining in a protective atmosphere.
Further, the average particle size of the nano zirconia is 12-18nm, and the average particle size of the nano ceria is 16-22 nm.
Further, the soluble ferric salt is ferric nitrate, and the soluble copper salt is copper nitrate.
Further, the adding amount of the cetylpyridinium is 1.15-1.65 times of the carrier, the adding amount of the PEG-600 is 1.38-2.1 times of the carrier, and the mass ratio of the cetylpyridinium to the PEG-600 is 1:1.2-1: 1.3.
Further, the addition amount of the cetyl pyridine is 1.42 times of the carrier by mass, and the addition amount of the PEG-600 is 1.78 times of the carrier by mass.
Further, the washing step includes a water washing step and an alcohol washing step.
Further, the processing time of the ultrasonic wave is more than 30 min.
The research of the invention shows that the proper amount of cetylpyridinium and PEG-600 are added into the carrier solution and the reaction temperature is kept so as to effectively improve the dispersibility of the carrier, prevent agglomeration and effectively improve the parameters of the specific surface area, pore volume, pore diameter and the like of the catalyst. This is because the carrier particles used in the present invention have a negative charge in a solution, and thus are first dispersed using a cationic surfactant, but after the hydrophilic group of the cationic surfactant is bonded to the carrier particles, the hydrophobic group protrudes into water to cause sedimentation, and based on this, the present invention uses a nonionic surfactant to perform secondary dispersion, thereby obtaining stable dispersed particles. In addition, the invention finds that the type and the content of the surfactant have obvious difference on the dispersion effect of the carrier particles through research, and the research finds that when the cationic surfactant is selected to be cetylpyridinium and the nonionic surfactant is selected to be PEG-600, the content is controlled to be 1.15-1.65 times of the addition amount of the cetylpyridinium and 1.38-2.1 times of the addition amount of the PEG-600, and the mass ratio of the cetylpyridinium to the PEG-600 is 1:1.2-1:1.3, so that the ideal dispersion effect is achieved.
Researches show that the dispersion effect of the carrier can be influenced by the reaction temperature and the pH value of the solution, the electrostatic repulsive force among particles can be reduced when the pH value is too large or too small, and based on the reaction system disclosed by the invention, a great amount of experiments show that the dispersion effect can be good when the pH value of the system is controlled to be 9-11. In addition, for the secondary dispersion system, too high reaction temperature may cause the surfactant to be dissociated from a stable state, resulting in poor dispersion effect, and too low reaction temperature may affect the growth rate of the carrier, thereby affecting the particle size uniformity and the dispersion uniformity. Based on the system of the present invention, it is necessary to control the reaction temperature at 55-75 ℃.
Compared with the prior art, the catalyst prepared by controlling the proper component proportion and reaction conditions has ideal specific surface area, pore volume and pore diameter and shows ideal catalytic effect.
Detailed Description
In order to better explain the present invention and to facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only illustrative of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims. The present invention will be further described with reference to the following examples.
Example 1
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 12nm and 0.24g of nano cerium oxide with the particle size of 16nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an alkaline solution to adjust the pH value of the solution to 9, heating the solution to 55 ℃, adding 0.74g of cetylpyridinium, carrying out constant temperature ultrasonic stirring for 35min, then respectively adding 0.9g of PEG-600, 0.07g of ferric nitrate and 0.17g of cupric nitrate, and continuously keeping the constant temperature ultrasonic stirring at 55 ℃ for 35min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, water washing, alcohol washing, drying, and calcining at 500 ℃ for 4 hours in a protective atmosphere to obtain the iron-based denitration catalyst.
Example 2
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 14nm and 0.26g of nano cerium oxide with the particle size of 20nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an alkaline solution to adjust the pH value of the solution to 10, heating the solution to 65 ℃, adding 0.86g of cetylpyridine, carrying out constant temperature ultrasonic stirring for 40min, then respectively adding 1.08g of PEG-600, 0.08g of ferric nitrate and 0.23g of copper nitrate, and continuously keeping constant temperature ultrasonic stirring at 65 ℃ for 40min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, water washing, alcohol washing and drying, and calcining at 500 ℃ for 4.5 hours in a protective atmosphere to obtain the iron-based denitration catalyst.
Example 3
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 17nm and 0.32g of nano cerium oxide with the particle size of 22nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an alkaline solution to adjust the pH value of the solution to 11, heating the solution to 75 ℃, adding 1.08g of cetylpyridine, carrying out constant temperature ultrasonic stirring for 45min, then respectively adding 1.4g of PEG-600, 0.11g of ferric nitrate and 0.31g of copper nitrate, and continuously keeping the constant temperature ultrasonic stirring at 75 ℃ for 45min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, washing with water, washing with alcohol, drying, and calcining at 560 ℃ for 5 hours under a protective atmosphere to obtain the iron-based denitration catalyst.
Example 4
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 17nm and 0.31g of nano cerium oxide with the particle size of 22nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an alkaline solution to adjust the pH value of the solution to 11, heating the solution to 75 ℃, adding 1g of cetylpyridine, carrying out constant temperature ultrasonic stirring for 45min, then respectively adding 1.26g of PEG-600, 0.07g of ferric nitrate and 0.23g of copper nitrate, and continuously keeping the constant temperature ultrasonic stirring at 75 ℃ for 45min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, water washing, alcohol washing, drying, and calcining at 520 ℃ for 4 hours under a protective atmosphere to obtain the iron-based denitration catalyst.
Comparative example 1
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 12nm and 0.24g of nano cerium oxide with the particle size of 16nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an alkaline solution to adjust the pH value of the solution to 9, heating the solution to 55 ℃, adding 0.6g of cetylpyridine, carrying out constant temperature ultrasonic stirring for 35min, then respectively adding 0.64g of PEG-600, 0.07g of ferric nitrate and 0.17g of copper nitrate, and continuously keeping constant temperature ultrasonic stirring at 55 ℃ for 35min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, water washing, alcohol washing, drying, and calcining at 500 ℃ for 4 hours in a protective atmosphere to obtain the iron-based denitration catalyst.
Comparative example 2
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 12nm and 0.24g of nano cerium oxide with the particle size of 16nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an acidic solution to adjust the pH value of the solution to be 5, heating the solution to 55 ℃, adding 0.74g of cetylpyridinium, carrying out constant temperature ultrasonic stirring for 35min, then respectively adding 0.9g of PEG-600, 0.07g of ferric nitrate and 0.17g of cupric nitrate, and continuously keeping the constant temperature ultrasonic stirring at 55 ℃ for 35min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, water washing, alcohol washing, drying, and calcining at 500 ℃ for 4 hours in a protective atmosphere to obtain the iron-based denitration catalyst.
Comparative example 3
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 17nm and 0.32g of nano cerium oxide with the particle size of 22nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an alkaline solution to adjust the pH value of the solution to be 11, adding 1.08g of cetyl pyridine at room temperature, carrying out constant temperature ultrasonic stirring for 45min, then respectively adding 1.4g of PEG-600, 0.11g of ferric nitrate and 0.31g of copper nitrate, and continuously carrying out ultrasonic stirring for 45min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, washing with water, washing with alcohol, drying, and calcining at 560 ℃ for 5 hours under a protective atmosphere to obtain the iron-based denitration catalyst.
Comparative example 4
A method for preparing an iron-based denitration catalyst, the method comprising the steps of:
1) mixing 0.4g of nano zirconia with the particle size of 17nm and 0.31g of nano cerium oxide with the particle size of 22nm, adding the mixture into 80mL of deionized water, slowly dropwise adding an alkaline solution to adjust the pH value of the solution to 11, heating the solution to 105 ℃, adding 1g of cetylpyridine, carrying out constant temperature ultrasonic stirring for 45min, then respectively adding 1.26g of PEG-600, 0.07g of ferric nitrate and 0.23g of copper nitrate, and continuously keeping the constant temperature ultrasonic stirring at 105 ℃ for 45min in the period;
2) and (3) subjecting the solution to vacuum evaporation at 180 ℃, cooling, water washing, alcohol washing, drying, and calcining at 520 ℃ for 4 hours under a protective atmosphere to obtain the iron-based denitration catalyst.
The test method comprises the following steps:
1. specific surface area and pore Structure determination
The specific surface area and the pore size are measured by a V-sorb 2800TP analyzer, the specific surface area is measured by a BET method, and the average pore size and the pore volume are calculated by a BJH method.
2. Evaluation of catalytic conditions and Activity
Grinding, tabletting and screening a selected catalyst sample to obtain particles with the size of 40-60 meshes, and putting the particles into a quartz tube, wherein the selected catalysis conditions are as follows: NO 500ppm, NH 3500 ppm, O23 vol.%, and N as carrier gas2The total flow rate of the gas is 210 mL/min, namely the space velocity is 10000 h-1. The reaction temperature was controlled by a temperature programmed controller and set at 5 ℃/min.
And (3) testing results:
the above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. An iron-based denitration catalyst, which is characterized in that: the catalyst comprises a carrier and a substrate, wherein the carrier comprises zirconium oxide and cerium oxide, the substrate comprises iron oxide and copper oxide, the mass ratio of the zirconium oxide to the cerium oxide is 1:0.6-1:0.8, the loading amount of iron is 5-7% by mass, the loading amount of copper is 7.5-22% by mass, the mass ratio of the iron loading amount to the copper loading amount is 1:2.5-1:4, and the specific surface area of the catalyst is 267-308m2The pore volume of the catalyst is 0.42-0.48cm2The pore diameter of the catalyst is 16.44-18.28 nm.
2. The iron-based denitration catalyst according to claim 1, wherein: the zirconium oxide is zirconium dioxide, and the cerium oxide is cerium oxide.
3. An iron-based denitration catalyst according to claim 1 or 2, wherein: the mass ratio of the zirconium oxide to the cerium oxide was 1: 0.78.
4. An iron-based denitration catalyst according to claim 1 or 2, wherein: the loading amount of the iron is 5% by mass, and the loading amount of the copper is 16.5% by mass.
5. An iron-based denitration catalyst according to claim 1 or 2, wherein: the specific surface area of the catalyst is 308m2The pore volume of the catalyst is 0.48cm2The pore diameter of the catalyst is 16.44 nm.
6. A method for preparing the iron-based denitration catalyst according to any one of claims 1 to 5, wherein: the method comprises the following steps:
1) preparing the raw materials according to the components and the content, wherein the zirconium source and the cerium source are respectively nano zirconium oxide and nano cerium oxide, and the iron source and the copper source are respectively soluble iron salt and soluble copper salt;
2) adding the nano zirconia and the nano cerium oxide with the contents into a deionized water solution, slowly dropwise adding an alkaline solution to adjust the pH of the solution to 9-11, heating to 55-75 ℃, adding cetylpyridine, carrying out constant temperature ultrasonic stirring for a certain time, then respectively adding PEG-600, soluble ferric salt and soluble copper salt, and continuously keeping constant temperature ultrasonic stirring at 55-75 ℃ in the period;
3) and (3) drying the solution by vacuum evaporation, washing, drying and calcining in a protective atmosphere.
7. A method as claimed in claim 6, characterized by: the addition amount of the cetylpyridinium is 1.15-1.65 times of the carrier, the addition amount of the PEG-600 is 1.38-2.1 times of the carrier, and the mass ratio of the cetylpyridinium to the PEG-600 is 1:1.2-1: 1.3.
8. A method as claimed in claim 7, wherein: the addition amount of the cetyl pyridine is 1.42 times of the carrier by mass, and the addition amount of the PEG-600 is 1.78 times of the carrier by mass.
9. A method according to claim 6 or 7, characterized by: the washing step comprises water washing and alcohol washing steps.
10. A method according to claim 6 or 7, characterized by: the soluble ferric salt is ferric nitrate and the soluble copper salt is cupric nitrate.
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