CN112044439A - Supported metal composite oxide SCR catalyst and preparation method thereof - Google Patents
Supported metal composite oxide SCR catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002905 metal composite material Substances 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- ZSVHLJKHZPBGHP-UHFFFAOYSA-N copper iron titanium Chemical compound [Fe][Ti][Cu] ZSVHLJKHZPBGHP-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229940076286 cupric acetate Drugs 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 239000012692 Fe precursor Substances 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KJRXZKWRJVRHLT-UHFFFAOYSA-N [O-2].[Ti+4].[Fe+2].[Cu+2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ti+4].[Fe+2].[Cu+2].[O-2].[O-2].[O-2] KJRXZKWRJVRHLT-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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Abstract
A supported metal composite oxide SCR catalyst and a preparation method thereof belong to the technical field of SCR catalyst preparation. The method comprises the following steps: (1) firstly, weighing raw materials, dissolving the raw materials in deionized water, and mixing, wherein the mixing process can be carried out by means of stirring, grinding, ball milling and the like, wherein the weight ratio of Fe: cu: the molar ratio of Ti is: 0.1-0.3: 0.1-0.2: 0.1. (2) And heating the mixture in a microwave field at the temperature of 60-100 ℃ and the power of 600-950W. (3) Transferring the mixture to a muffle furnace for roasting at the roasting temperature: the roasting time is 3-6 h at 400-800 ℃. The invention has the advantages of simple and easily obtained raw materials, easily controlled preparation conditions, no toxicity and no harm, and the obtained catalyst has good catalytic activity.
Description
Technical Field
The invention belongs to the technical field of preparation of SCR catalysts, and particularly relates to an iron-copper-titanium composite metal oxide denitration catalyst and a preparation method thereof.
Background
Nitrogen Oxides (NO)X) The environment-friendly pollution-free agent is a main pollutant in the current air pollution, mainly comes from the emission of fixed sources and mobile sources such as power plants, factories, automobile exhaust, combustion of fossil fuels and the like, is a main reason for forming greenhouse effect, acid rain, photochemical smog and PM2.5, and has obvious influence on the global environment and human health. And for Nitrogen Oxides (NO)X) By removal of ammonia (NH)3) SCR process as a reductant (i.e. NH)3-SCR) has been of interest and has found widespread commercial application in the removal of nitrogen oxides from stationary and mobile sources.
The catalyst is used for efficiently and selectively removing NO in SCR technologyXConversion to N2The most widely used catalyst system at present is V2O5-WO3(MoO3)/TiO2And has higher removal efficiency at the temperature of 300-400 ℃. However, the traditional V-based catalyst has certain limitation at low temperature, is easily poisoned by alkali/alkaline earth metal, phosphorus and heavy metal in flue gas to gradually deactivate, and simultaneously, the active component V of the traditional V-based catalyst2O5Is itself biologically toxic. Therefore, it is very important to modify the traditional catalyst and invent a new catalyst.
In order to overcome the disadvantages and problems of the above catalysts, and also to consider the problems of economic operation cost, etc., iron-based non-noble metal catalysts have received much attention. Iron-based catalysts have been widely studied because of their high activity, high stability, low toxicity, and certain economic benefits. Because of the narrow temperature window of pure iron-based catalysts, especially the non-ideal low temperature activity, the modification of iron-based catalysts is of great interest (Sun, j.et al.ind.eng.chem.res.2017,56, 12101-. Sun et al investigated Ti4+、Ce3+/4+、Al3+Effect of doping on the activity of iron-based catalysts. It was found that Ti4+The doped catalyst shows the highest activity due to strong acidity, moderate reducibility and the like. Indicates Ti4+The addition of the catalyst can improve the SCR activity of the catalyst and has certain promotion effect on the reaction. Meanwhile, the Chinese patent CN101380578A discloses a method for synthesizing NH3Selective catalytic reduction of NO for a reductantXThe iron-titanium composite oxide catalyst has higher activity, high stability, selectivity and SO resistance at the temperature of 250-400 DEG C2Capability, no toxicity and no harm.
Due to the increasing demand for catalyst temperature window and performance, it is desirable to improve the SCR performance of the catalyst by modifying the catalyst, for example, patent CN106732646A discloses a catalyst in which manganese oxide is supported on a ferro-titanium catalyst by an impregnation method.
The invention combines chemical precipitation and microwave assistance to prepare MTiOxSCR catalyst on carrier (M ═ Fe, Cu) with TiO2And the active components and the Ti source are simultaneously introduced to the surface of the carrier, so that the low-temperature activity and the sulfur resistance of the catalyst are improved. The used materials are economical, environment-friendly, non-toxic and harmless, and the preparation process is simple, easy to repeat and wide in application range, so that the preparation method has good applicability.
According to the literature report, the preparation of the iron-based catalyst is mainly carried out by using the traditional coprecipitation method or impregnation method, and the performance of the iron-based catalyst is improved by adding metal elements, for example, patent CN109331835A discloses a method for solving the limitation of the weak water resistance of the copper-iron-titanium oxide catalyst by adding other metal elements by adopting the coprecipitation method.
The method described by the invention utilizes the advantages of high heating speed, uniformity, no contact heating and no temperature gradient of the microwave, so that the catalyst forms uniform high-dispersion particles in a microwave field. Firstly, physically mixing the raw materials according to a stoichiometric ratio, heating the mixture in a microwave field after uniformly mixing, and roasting the obtained mixture at a specific temperature to obtain the required catalyst. To date, no document or patent reports the application of the iron-copper-titanium catalyst in SCR reaction.
Disclosure of Invention
The invention aims to provide a preparation method of an iron-copper-titanium catalyst, which adopts a method of combining chemical precipitation and a microwave field and realizes the preparation of a target catalyst by roasting. The catalyst performance is improved through uniform heating, the low-temperature activity of the catalyst is improved, and meanwhile, the temperature window is further widened.
The preparation method of the iron-copper-titanium catalyst mainly comprises the following steps:
(1) firstly weighing Fe precursor, Ti precursor, Cu precursor raw material and carrier, dissolving in deionized water and mixing to obtain mixed salt solution, wherein in the mixing process, stirring, water bath heating and other means can be used, wherein the weight ratio of Fe: cu: the molar ratio of Ti is: 0.1-0.3: 0.1-0.2: 0.1.
(2) Ultrasonically treating the uniformly mixed water solution sample, heating the water solution sample in microwave at the temperature of 60-100 ℃ and the power of 600-950W, and then drying the water solution sample in an oven;
(3) and transferring the dried sample to a muffle furnace for roasting at 400-800 ℃ for 3-6 h to obtain the target catalyst sample.
The addition amount of each element in the catalyst can be adjusted according to the addition amount of the raw material in the step (1).
The preparation method of the iron-copper-titanium catalyst for SCR reaction is characterized by comprising the following steps: firstly, weighing raw materials according to a stoichiometric number, dissolving and ultrasonically treating the raw materials, placing the raw materials in microwave for heating and drying, and roasting at 400-800 ℃ to obtain the target catalyst.
The preparation method of the iron-copper-titanium catalyst for SCR reaction is characterized by comprising the following steps: after the sample is dissolved, the microwave is used for catalyzing and heating, so that non-contact uniform heating is realized, the catalyst is uniformly mixed, and the high-dispersion particles are obtained.
The precursor of Fe can be one or more of Fe-containing salts and ferric oxide, and the Fe-containing salts are selected from ferric nitrate, ferric sulfate, ferric chloride and the like;
the precursor of Ti can be one or more of Ti-containing salts and metatitanic acid, and the Ti-containing salts can be titanyl sulfate, titanium sulfate and the like;
the precursor of Cu can be one or more of Cu-containing salts and copper oxide, and the Cu-containing salts comprise copper sulfate, copper nitrate, copper chloride, copper acetate and the like.
The carrier can be one or more of a titanium dioxide carrier, a silica gel carrier and an alumina carrier.
To further ensure the dissolution and mixing of the solids, organic dispersants such as EDTA may be added during the mixing of the precursors. The mol ratio of the addition amount to Fe is as follows: 1: 1 to 2.
The invention has the following advantages:
1. the raw materials used in the invention have low price, simple preparation, wide application range, no toxicity and no harm to the environment and human health;
2. in the preparation process, a microwave catalytic heating method is adopted, so that the mixing degree of the precursor is increased, the formation of high-dispersion particles is promoted, and the catalytic activity is increased.
3. The iron-copper-titanium catalyst prepared by the invention has good low-temperature catalytic activity, widens the temperature window, keeps higher activity in a certain temperature range, and has good application prospect in the field of NOx emission control, for example, the NO conversion rate is basically 100% in the temperature range of 260-350 ℃.
Drawings
FIG. 1 is an XRD spectrum of sample # 1 prepared in example 1;
FIG. 2 is an XRD spectrum of sample No. 2 prepared in example 2;
FIG. 3 is an XRD spectrum of samples No. 3 and No. 4 prepared in example 3 and example 4;
fig. 4 shows the SCR activity evaluation results of catalyst samples # 1 in example 1, # 2 in example 2, and # 4 in example 4.
Detailed Description
The present invention will be described with reference to examples, but the present invention is not limited to the examples.
Example 1 (comparative):
accurately weighing titanyl sulfate with the mass of 1.30gPowder, dissolved in a certain amount of deionized water. 2.65g Fe (NO) are weighed out3)3·9H2O, adding into the solution, dissolving, and adding 20g of TiO2And (5) powder and uniform mixing. And (3) carrying out ultrasonic treatment on the mixed solution for 0.5h, then placing the mixed solution in a microwave field for heating, controlling the input power to be 600-950W, and then transferring the sample into a muffle furnace to be roasted for 3h at 500 ℃ to obtain the No. 1 catalyst.
Example 2 (comparative):
accurately weighing titanyl sulfate powder with the mass of 1.23g, dissolving in a certain amount of deionized water, and weighing 1.52g of Cu (NO)3)2·3H2O, adding into the solution, dissolving, and adding 20g of TiO2And (5) powder and uniform mixing. And (3) carrying out ultrasonic treatment on the mixed solution for 0.5h, then placing the mixed solution in a microwave field for heating, controlling the input power to be 600-950W, and then transferring the sample into a muffle furnace to be roasted for 3h at 500 ℃ to obtain the 2# catalyst.
Example 3:
accurately weighing titanyl sulfate powder with mass of 0.81g, dissolving in deionized water, and weighing 0.84g Fe (NO)3)3·9H2O and 1.01gCu (NO)3)2·3H2Adding O into the solution, stirring to dissolve completely, adding 20g of TiO after dissolving2And (5) powder and uniform mixing. And (3) carrying out ultrasonic treatment on the mixed solution for 0.5h, then placing the mixed solution in a microwave field for heating, controlling the input power to be 600-950W, and then transferring the sample into a muffle furnace to be roasted for 3h at 500 ℃ to obtain the 3# catalyst.
Example 4:
accurately weighing titanyl sulfate powder with mass of 0.61g, dissolving in deionized water, and weighing 1.26g Fe (NO)3)3·9H2O and 0.76gCu (NO)3)2·3H2Adding O into the solution, stirring to dissolve completely, adding 20g of TiO after dissolving2And (5) powder and uniform mixing. And (3) carrying out ultrasonic treatment on the mixed solution for 0.5h, then placing the mixed solution in a microwave field for heating, controlling the input power to be 600-950W, and then transferring the sample into a muffle furnace to be roasted for 3h at 500 ℃ to obtain the No. 4 catalyst.
Example 5:
accurately weighing the powder with the mass of 0.61g of titanyl sulfate powder, dissolved in a certain amount of deionized water, 0.63g of Fe (NO) was weighed3)3·9H2O and 01.51gCu (NO)3)2·3H2Adding O into the solution, stirring to dissolve completely, adding 20g of TiO after dissolving2And (5) powder and uniform mixing. And (3) carrying out ultrasonic treatment on the mixed solution for 0.5h, then placing the mixed solution in a microwave field for heating, controlling the input power to be 600-950W, and then transferring the sample into a muffle furnace to be roasted for 3h at 500 ℃ to obtain the 5# catalyst.
Test example 1:
x-ray diffraction tests (Smartlab SE, Rigaku corporation) were performed on the catalyst # 1 of example 1, the catalyst # 2 of example 2, the catalyst # 3 of example 3, and the catalyst # 4 of example 4, respectively, and the results are shown in fig. 1, fig. 2, and fig. 3. Wherein the sample # 1 in fig. 1 corresponds to the catalyst # 1 of example 1, the sample # 2 in fig. 2 corresponds to the catalyst # 2 of example 2, and the samples # 3 and # 4 in fig. 3 correspond to the catalysts # 3 and # 4 of example 3 and example 4. The results show that the main phases of the 1#, 2#, 3#, and 4# catalysts are anatase, and no other diffraction peaks are found, which indicates that the main phases are well dispersed on the surface of the carrier.
Test example 2:
the catalyst # 1 of example 1, the catalyst # 2 of example 2 and the catalyst # 4 of example 4 were subjected to SCR activity tests, respectively, and the composition of the raw material gas was NO (700ppm), NH3(700ppm)、O2(5.0％)、N2Or He balance, reaction space velocity of 30000h-1. Heating the reactor from room temperature to 500 deg.C at 40 deg.C/min, maintaining at 20 deg.C, stabilizing for 10min, and detecting NO and NO in NOx analyzer (42i-HL, Thermo) after the simulated gas passes through the catalyst2The concentration of (c) is varied. According to the detection result, the 1# catalyst has better activity in a high-temperature area, but relatively poorer low-temperature activity, and after Cu is added, the obtained 4# catalyst effectively improves the low-temperature activity, has higher SCR catalytic activity at 260 ℃ and is maintained within 260-350 ℃. TiO 22The addition of (b) helps to improve the sulfur resistance of the catalyst. The test results are shown in FIG. 4, in which (1#) (2#) (4#) corresponds to the catalyst # 1 of example 1, the catalyst # 2 of example 2, and the catalyst # 4 of example 4, respectively。
Claims (10)
1. A preparation method of a supported metal composite oxide SCR catalyst is characterized by comprising the following steps:
(1) firstly, weighing a precursor of Fe, a precursor of Ti, a precursor raw material of Cu and a carrier, dissolving in deionized water and mixing to obtain a mixed salt solution, wherein the weight ratio of Fe: ti: the molar ratio of Cu is: 0.1-0.3: 0.1-0.2: 0.1;
(2) ultrasonically treating the uniformly mixed sample, and then heating the sample in a microwave field, wherein the heating temperature is 60-100 ℃, and the power is 600-950W;
(3) and transferring the mixed sample to a muffle furnace for roasting at the roasting temperature of 400-800 ℃ for 3-6 h to obtain the target catalyst sample.
2. The preparation method of the supported metal composite oxide SCR catalyst according to claim 1, wherein the precursor of Fe is one or more of Fe-containing salts and iron oxide; the precursor of Ti is one or more of Ti-containing salts and metatitanic acid; the precursor of Cu is one or more of Cu-containing salts and copper oxide.
3. The method of claim 2, wherein the Fe-containing salt is selected from the group consisting of ferric nitrate, ferric sulfate, and ferric chloride.
4. The method of claim 2, wherein the Ti-containing salts are selected from titanyl sulfate and titanium sulfate.
5. The method of claim 1, wherein the copper-containing salt is selected from the group consisting of ferric sulfate, cupric nitrate, cupric chloride, and cupric acetate.
6. The method for preparing an iron-copper-titanium catalyst for SCR reaction as recited in claim 1, wherein the carrier is one or more selected from the group consisting of titanium dioxide, silica gel, and alumina.
7. The method for preparing a supported metal composite oxide SCR catalyst according to claim 1, wherein an organic dispersant is added during the precursor dissolving and mixing process in the step (1), and the molar ratio of the added amount to Fe is 1: 1 to 2.
8. The method of claim 7, wherein the organic dispersant is EDTA.
9. An iron-copper-titanium catalyst prepared according to the process of any one of claims 1 to 8.
10. Use of the iron-copper-titanium catalyst prepared by the method according to any one of claims 1 to 8 in an SCR reaction at a reaction temperature of 260 to 350 ℃ with a NO conversion of substantially 100%.
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