WO2021000458A1 - Method for preparing cerium silicon composite oxide, and product and application thereof - Google Patents
Method for preparing cerium silicon composite oxide, and product and application thereof Download PDFInfo
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- WO2021000458A1 WO2021000458A1 PCT/CN2019/112305 CN2019112305W WO2021000458A1 WO 2021000458 A1 WO2021000458 A1 WO 2021000458A1 CN 2019112305 W CN2019112305 W CN 2019112305W WO 2021000458 A1 WO2021000458 A1 WO 2021000458A1
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- composite oxide
- cerium
- silicon composite
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- ammonium nitrate
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- RBZGEUJLKTVORU-UHFFFAOYSA-N 12014-84-5 Chemical compound [Ce]#[Si] RBZGEUJLKTVORU-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000003546 flue gas Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011593 sulfur Substances 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 231100000572 poisoning Toxicity 0.000 abstract description 8
- 230000000607 poisoning effect Effects 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 2
- 238000003483 aging Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000001069 Raman spectroscopy Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- -1 cerium ammonium nitrate ethanol Chemical compound 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Definitions
- the invention belongs to the field of flue gas denitration catalysts, and specifically relates to a preparation method of a cerium-silicon composite oxide and its products and applications.
- the most mature commercial catalyst used to catalyze the NH 3 -SCR reaction is the V 2 O 5 -WO 3 (MoO 3 )/TiO 2 catalyst.
- the catalyst has good activity in the middle and high temperature section (300-400°C).
- its N 2 selectivity is poor in the middle and high temperature section, and its activity in the low temperature section is not ideal.
- V 2 O 5 is also biologically toxic.
- CeO 2 has a special octahedral configuration, which is easy to produce oxygen defects in the crystal, so it has good redox ability. And Ce, as the rare earth element with the largest reserves, is relatively cheap. CeO 2 has been used as an auxiliary, carrier or active component in the NH 3 -SCR field, but the surface of pure CeO 2 is weaker and has a smaller specific surface area. Incorporating SiO 2 into Ce/TiO 2 or V/TiO 2 can effectively increase the acid sites of the catalyst, increase the specific surface area of the catalyst, and further enhance the NH 3 -SCR activity of the catalyst. Moreover, neither CeO 2 nor SiO 2 has biological toxicity, and CeO 2 also exhibits good sulfur resistance potential. Therefore, the cerium-silicon composite oxide combining CeO 2 and SiO 2 may be a potential NH 3 -SCR catalyst with good application prospects.
- the objective of the present invention is to provide a method for preparing a cerium-silicon composite oxide, which has simple raw materials, low cost and simple method.
- Another object of the present invention is to provide a cerium-silicon composite oxide as a flue gas denitration catalyst with better low-temperature activity, high N 2 selectivity, and superior sulfur poisoning resistance, which can be used in flue gas denitration in coal-fired power plants.
- a preparation method of cerium-silicon composite oxide includes the following steps:
- Step 1) Add concentrated ammonia water dropwise to the resulting mixed solution under stirring to cause precipitation and aging precipitation;
- Step 2) The obtained precipitate is filtered, washed, dried and calcined to obtain a cerium-silicon composite oxide.
- the concentration of the cerium ammonium nitrate ethanol solution is 0.005 mol/L to 0.2 mol/L.
- the duration of the continued stirring is 1 h.
- the dropping of concentrated ammonia water is stopped when the pH of the mixed solution is 10, and the concentration of the concentrated ammonia water is 13.2 mol/L.
- the time for the aging precipitation is 12h.
- the washing is 3 times with deionized water, and the drying is drying in an oven at 100° C. for 12 hours.
- the roasting is in a muffle furnace with a temperature of 550°C and a duration of 4 hours.
- the cerium-silicon composite oxide is obtained by the preparation method of the cerium-silicon composite oxide.
- the cerium-silicon composite oxide is Ce-2Si.
- cerium-silicon composite oxide as a flue gas denitration catalyst.
- both cerium ammonium nitrate and TEOS can be dissolved in ethanol, and after adding concentrated ammonia to the solution, both cerium ammonium nitrate and TEOS can be hydrolyzed and precipitated quickly, so the co-precipitation method is adopted to combine the cerium ammonium nitrate and TEOS in After dissolving and mixing uniformly in ethanol, an excessive amount of ammonia is added dropwise to make the precipitation complete, and then the cerium-silicon composite oxide catalyst can be prepared by aging, washing, drying and roasting.
- the method for preparing a cerium-silicon composite oxide provided by the present invention has simple raw materials, low cost, environmentally friendly, simple preparation method, and large-scale production;
- the cerium-silicon composite oxide provided by the present invention has a larger specific surface area, stronger acidity and special surface adsorption mechanism due to the doping of SiO 2 , which effectively improves the CeO 2
- the NH 3 -SCR activity further improves the water and sulfur resistance of the catalyst; as a flue gas denitration catalyst, the cerium-silicon composite oxide has good activity at medium and low temperatures, high N 2 selectivity, superior sulfur poisoning resistance, and environmentally friendly , Has a wide range of industrial application prospects.
- Figure 1 shows the X-ray diffraction (XRD) results of the cerium-silicon composite oxide catalyst and pure CeO 2 ;
- Figure 2 is a graph showing the results of Raman spectra of the cerium-silicon composite oxide catalyst and pure CeO 2 ;
- Figure 3 is the result of the NH 3 -SCR reaction between a cerium-silicon composite oxide catalyst and pure CeO 2 , where (a) is the NO conversion rate and (b) is the N 2 selectivity;
- Figure 4 is a graph showing the test results of the sulfur resistance of the cerium-silicon composite oxide catalyst at 250°C.
- XRD X-ray diffraction
- Raman spectroscopy Raman spectroscopy
- NH 3 -SCR reaction catalytic performance test
- sulfur poisoning performance test sulfur poisoning performance test and other characterization methods to evaluate its bulk structure and catalytic performance
- Fig. 1 The XRD results in Fig. 1 show that within the range of the feed concentration mentioned in the present invention, Ce and Si can be mixed together well, the degree of crystallization of CeO 2 is very low, and SiO 2 reduces the degree of crystallization of CeO 2 .
- the result of Raman in Fig. 2 also shows that the crystal structure of CeO 2 is destroyed, a strong interaction occurs between CeO 2 and SiO 2 and the oxygen defect concentration increases.
- the result of the NH 3 -SCR reaction in Figure 3 shows that the catalytic performance of the cerium-silicon composite oxide catalyst is significantly better than that of CeO 2.
- the NO conversion rate of the cerium-silicon composite oxide is as high as about 90%, and its N 2 selectivity is close to 100%.
- the NO conversion rate of pure CeO 2 is less than 30%, and the N 2 selectivity decreases rapidly as the temperature increases.
- XRD results in Figure 1 show that Ce and Si can be mixed together well within the feeding concentration range mentioned in the present invention.
- the degree of crystallization of CeO 2 is very high. Low, SiO 2 reduces the crystallinity of CeO 2 .
- the result of Raman in Fig. 2 also shows that the crystal structure of CeO 2 is destroyed, a strong interaction occurs between CeO 2 and SiO 2 and the oxygen defect concentration increases.
- the results of the NH 3 -SCR reaction in Figure 3 show that the catalytic performance of the cerium-silicon composite oxide catalyst is significantly better than that of CeO 2.
- the NO conversion rate of the cerium-silicon composite oxide is as high as about 90%, and its N 2 selectivity is close to 100%.
- the NO conversion rate of pure CeO 2 is less than 30%, and the N 2 selectivity decreases rapidly as the temperature increases.
- Figure 4 shows that the cerium-silicon composite oxide exhibits excellent sulfur poisoning resistance at 250°C, and the NO conversion rate has been stable above 90% for a long time without a significant downward trend. However, the NO conversion rate of CeO 2 has dropped seriously, showing Obvious characteristics of sulfur poisoning.
- Example 7 Determination of catalytic performance of cerium-silicon composite oxide for denitration
- the prepared cerium-silicon composite oxide catalyst was applied to the NH 3 -SCR reaction, and the specific reaction conditions were as follows: the catalytic reaction test was carried out in a fixed-bed continuous flow quartz reactor. The particle size of the catalyst is 60-80 mesh, and the dosage is 250 mg.
- the reaction gas composition is: 500 ppm NO, 500 ppm NH 3 , 200 ppm SO 2 , 5% O 2 , and N 2 as the balance gas, and the gas space velocity in the reaction is 30000 mL ⁇ g -1 ⁇ h -1 . Before the reaction, the catalyst needs to be purged with high purity N 2 at 200°C for 1 h.
- the catalytic reaction is carried out at 50-450°C, and the activity data is collected after the reaction reaches equilibrium.
- the product was detected and analyzed by Thermofisher IS10 FTIR, and the NO conversion rate and N 2 selectivity were calculated by the following formula:
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Abstract
A method for preparing a cerium silicon composite oxide, and a product and an application thereof. According to the method, ceric ammonium nitrate and tetraethyl orthosilicate (TEOS) are mixed and dissolved in ethyl alcohol, then under a stirring condition, stronger ammonia water is dropwise added until precipitation is complete, and then the cerium silicon composite oxide is obtained through ageing, filtering, washing, drying and calcining. Compared with pure CeO2, the cerium silicon composite oxide has a larger specific surface area, higher acidity, and a special surface adsorption mechanism, and the activity of CeO2 for catalyzing an NH3-SCR reaction is effectively improved. The cerium silicon composite oxide serves as a flue gas denitration catalyst, and has better medium and low temperature activity, high N2 selectivity, superior sulfur poisoning resistance, and environmental friendliness. The method for preparing the cerium silicon composite oxide is simple, raw materials are simple and easy to obtain, and the cerium silicon composite oxide can be produced in a large scale and has a broad industrial application prospect.
Description
本发明属于烟气脱硝催化剂领域，具体涉及一种铈硅复合氧化物的制备方法及其产物和应用。The invention belongs to the field of flue gas denitration catalysts, and specifically relates to a preparation method of a cerium-silicon composite oxide and its products and applications.
近年来，大气污染问题越来越得到人们的重视，其中燃煤电厂烟气中的氮氧化物(NO
x)是污染的重要来源，对烟气进行脱硝处理刻不容缓。研究表明，NH
3选择性催化还原NO
x(NH
3-SCR)是燃煤电厂烟气脱硝最有效的办法，并已经成熟应用在烟气脱硝领域。
In recent years, people have paid more and more attention to the problem of air pollution. Among them, nitrogen oxides (NO x ) in the flue gas of coal-fired power plants are an important source of pollution, and it is urgent to denitrify the flue gas. Studies have shown that NH 3 selective catalytic reduction of NO x (NH 3 -SCR) is the most effective method for flue gas denitration in coal-fired power plants, and it has been maturely applied in the field of flue gas denitration.
现阶段，用于催化NH
3-SCR反应最成熟的商用催化剂是V
2O
5-WO
3(MoO
3)/TiO
2催化剂。该催化剂在中高温段(300-400℃)具有良好的活性。但是其在中高温段N
2选择性较差，低温段活性又不够理想，V
2O
5还具有生物毒性。基于以上原因，寻找一种具有优良活性和选择性且环境友好的不含钒催化剂正在成为新的研究热点。
At this stage, the most mature commercial catalyst used to catalyze the NH 3 -SCR reaction is the V 2 O 5 -WO 3 (MoO 3 )/TiO 2 catalyst. The catalyst has good activity in the middle and high temperature section (300-400°C). However, its N 2 selectivity is poor in the middle and high temperature section, and its activity in the low temperature section is not ideal. V 2 O 5 is also biologically toxic. For the above reasons, finding a vanadium-free catalyst with excellent activity and selectivity and environmentally friendly is becoming a new research focus.
CeO
2具有特殊的八面体构型，容易在晶体内产生氧缺陷，因而具有良好的氧化还原能力。且Ce作为储量最大的稀土元素，价格相对低廉。CeO
2作为助剂，载体或活性组分等已被应用在NH
3-SCR领域中，但纯CeO
2表面酸性较弱，比表面积较小。将SiO
2掺入Ce/TiO
2或V/TiO
2中可以有效增加催化剂的酸性位点，增大催化剂比表面积，进而提升催化剂的NH
3-SCR活性。且CeO
2和SiO
2均无生物毒性，CeO
2还体现出良好的抗硫潜力。因此，将CeO
2和SiO
2结合起来的铈硅复合氧化物可能是一种潜在的具有良好应用前景的NH
3-SCR催化剂。
CeO 2 has a special octahedral configuration, which is easy to produce oxygen defects in the crystal, so it has good redox ability. And Ce, as the rare earth element with the largest reserves, is relatively cheap. CeO 2 has been used as an auxiliary, carrier or active component in the NH 3 -SCR field, but the surface of pure CeO 2 is weaker and has a smaller specific surface area. Incorporating SiO 2 into Ce/TiO 2 or V/TiO 2 can effectively increase the acid sites of the catalyst, increase the specific surface area of the catalyst, and further enhance the NH 3 -SCR activity of the catalyst. Moreover, neither CeO 2 nor SiO 2 has biological toxicity, and CeO 2 also exhibits good sulfur resistance potential. Therefore, the cerium-silicon composite oxide combining CeO 2 and SiO 2 may be a potential NH 3 -SCR catalyst with good application prospects.
发明内容Summary of the invention
发明目的：针对现有技术存在的上述问题，本发明的目的在于提供一种铈硅复合氧化物的制备方法，原料简单易得，成本低廉，方法简便。本发明的另一目的在于提供铈硅复合氧化物，作为烟气脱硝催化剂，低温活性更好，N
2选择性高，抗硫中毒性能优越，可应用在燃煤电厂烟气脱硝中。
Objective of the invention: In view of the above-mentioned problems in the prior art, the objective of the present invention is to provide a method for preparing a cerium-silicon composite oxide, which has simple raw materials, low cost and simple method. Another object of the present invention is to provide a cerium-silicon composite oxide as a flue gas denitration catalyst with better low-temperature activity, high N 2 selectivity, and superior sulfur poisoning resistance, which can be used in flue gas denitration in coal-fired power plants.
技术方案：为了解决上述问题，本发明所采用的技术方案如下：Technical solution: In order to solve the above problems, the technical solution adopted by the present invention is as follows:
一种铈硅复合氧化物的制备方法，包括如下步骤：A preparation method of cerium-silicon composite oxide includes the following steps:
1)将硝酸铈铵溶于乙醇，得到的硝酸铈铵乙醇溶液，在搅拌下滴加正硅酸四乙酯(TEOS)，得到混合溶液，所述混合溶液中的硝酸铈铵和正硅酸四乙酯的摩尔比为4∶1-1∶4，继续搅拌；1) Dissolve cerium ammonium nitrate in ethanol to obtain an ethanol solution of cerium ammonium nitrate, and add tetraethyl orthosilicate (TEOS) dropwise with stirring to obtain a mixed solution. The mixed solution of cerium ammonium nitrate and tetraethylorthosilicate The molar ratio of ethyl ester is 4:1-1:4, continue to stir;
2)步骤1)所得混合溶液在搅拌下滴加浓氨水，产生沉淀，老化沉淀；2) Step 1) Add concentrated ammonia water dropwise to the resulting mixed solution under stirring to cause precipitation and aging precipitation;
3)步骤2)所得沉淀经过过滤，洗涤，干燥，焙烧，得到铈硅复合氧化物。3) Step 2) The obtained precipitate is filtered, washed, dried and calcined to obtain a cerium-silicon composite oxide.
优选地，所述硝酸铈铵乙醇溶液，其浓度为0.005mol/L～0.2mol/L。Preferably, the concentration of the cerium ammonium nitrate ethanol solution is 0.005 mol/L to 0.2 mol/L.
优选地，所述继续搅拌的时长为1h。Preferably, the duration of the continued stirring is 1 h.
优选地，所述滴加浓氨水至所述混合溶液的pH＝10时停止，所述浓氨水的浓度为13.2mol/L。Preferably, the dropping of concentrated ammonia water is stopped when the pH of the mixed solution is 10, and the concentration of the concentrated ammonia water is 13.2 mol/L.
优选地，所述老化沉淀的时间为12h。Preferably, the time for the aging precipitation is 12h.
优选地，所述洗涤是用去离子水洗涤3次，所述干燥是在100℃的烘箱中干燥12h。Preferably, the washing is 3 times with deionized water, and the drying is drying in an oven at 100° C. for 12 hours.
优选地，所述焙烧是在马弗炉中，温度为550℃，时长4h。Preferably, the roasting is in a muffle furnace with a temperature of 550°C and a duration of 4 hours.
所述的铈硅复合氧化物的制备方法得到的铈硅复合氧化物。The cerium-silicon composite oxide is obtained by the preparation method of the cerium-silicon composite oxide.
优选地，所述的铈硅复合氧化物，为Ce-2Si。Preferably, the cerium-silicon composite oxide is Ce-2Si.
所述的铈硅复合氧化物作为烟气脱硝催化剂的应用。The application of the cerium-silicon composite oxide as a flue gas denitration catalyst.
本发明的原理：由于硝酸铈铵和TEOS均能溶于乙醇，且向溶液中滴加浓氨水后硝酸铈铵和TEOS均能快速水解沉淀，因此采用共沉淀法，将硝酸铈铵和TEOS在乙醇中溶解并混合均匀后逐滴滴加过量的氨水，使其沉淀完全，然后经老化、洗涤、干燥、焙烧即可制得铈硅复合氧化物催化剂。The principle of the invention: Since both cerium ammonium nitrate and TEOS can be dissolved in ethanol, and after adding concentrated ammonia to the solution, both cerium ammonium nitrate and TEOS can be hydrolyzed and precipitated quickly, so the co-precipitation method is adopted to combine the cerium ammonium nitrate and TEOS in After dissolving and mixing uniformly in ethanol, an excessive amount of ammonia is added dropwise to make the precipitation complete, and then the cerium-silicon composite oxide catalyst can be prepared by aging, washing, drying and roasting.
有益效果：相比于现有技术，本发明的优点为：Beneficial effects: Compared with the prior art, the advantages of the present invention are:
(1)本发明提供的一种铈硅复合氧化物的制备方法，原料简单易得，成本低廉，环境友好，制备方法简便，可大规模生产；(1) The method for preparing a cerium-silicon composite oxide provided by the present invention has simple raw materials, low cost, environmentally friendly, simple preparation method, and large-scale production;
(2)本发明提供的铈硅复合氧化物，相较纯CeO
2，SiO
2的掺杂使其具有更大的比表面积，更强的酸性和特别的表面吸附机制，有效提升了CeO
2的NH
3-SCR活性，且进一步提升了催化剂的抗水抗硫性能；该铈硅复合氧化物作为烟气脱硝催化剂，中低温活性好，N
2选择性高，抗硫中毒性能优越，且环境友好，具有广泛的工业应用前景。
(2) Compared with pure CeO 2 , the cerium-silicon composite oxide provided by the present invention has a larger specific surface area, stronger acidity and special surface adsorption mechanism due to the doping of SiO 2 , which effectively improves the CeO 2 The NH 3 -SCR activity further improves the water and sulfur resistance of the catalyst; as a flue gas denitration catalyst, the cerium-silicon composite oxide has good activity at medium and low temperatures, high N 2 selectivity, superior sulfur poisoning resistance, and environmentally friendly , Has a wide range of industrial application prospects.
图1为铈硅复合氧化物催化剂和纯CeO
2的X射线衍射(XRD)结果图；
Figure 1 shows the X-ray diffraction (XRD) results of the cerium-silicon composite oxide catalyst and pure CeO 2 ;
图2为铈硅复合氧化物催化剂和纯CeO
2的拉曼光谱(Raman)结果图；
Figure 2 is a graph showing the results of Raman spectra of the cerium-silicon composite oxide catalyst and pure CeO 2 ;
图3为铈硅复合氧化物催化剂和纯CeO
2的NH
3-SCR反应结果图，其中(a)为NO转化率，(b)为N
2选择性；
Figure 3 is the result of the NH 3 -SCR reaction between a cerium-silicon composite oxide catalyst and pure CeO 2 , where (a) is the NO conversion rate and (b) is the N 2 selectivity;
图4为铈硅复合氧化物催化剂在250℃时的抗硫性能测试结果图。Figure 4 is a graph showing the test results of the sulfur resistance of the cerium-silicon composite oxide catalyst at 250°C.
下面结合具体实施例对本发明进一步进行描述。The present invention will be further described below in conjunction with specific embodiments.
实施例1：CeO
2催化剂的制备
Example 1: Preparation of CeO 2 catalyst
准确称取6.37g硝酸铈铵溶于150mL乙醇中，继续搅拌1h，然后在搅拌下逐滴滴加浓氨水到上述混合溶液中至pH＝10，使其沉淀完全，过夜老化12h后过滤，用去离子水洗涤3次，100℃的烘箱中干燥12h，然后在空气气氛下在马弗炉中经550℃焙烧4h，即制得CeO
2催化剂。其XRD、Raman、NH
3-SCR活性以及抗硫性能测试结果见图1-4。
Accurately weigh 6.37g of cerium ammonium nitrate and dissolve it in 150mL ethanol, continue to stir for 1h, and then add concentrated ammonia water dropwise under stirring to the above mixed solution to pH=10 to make the precipitation complete. After aging for 12h overnight, filter it. Washed with deionized water for 3 times, dried in an oven at 100°C for 12 hours, and then calcined in a muffle furnace at 550°C for 4 hours in an air atmosphere to obtain a CeO 2 catalyst. The XRD, Raman, NH 3 -SCR activity and sulfur resistance test results are shown in Figure 1-4.
实施例2：4Ce-Si催化剂的制备Example 2: Preparation of 4Ce-Si catalyst
准确称取6.37g硝酸铈铵溶于150mL乙醇中，搅拌下滴加0.65mL的TEOS，继续搅拌1h，然后在搅拌下逐滴滴加浓氨水到上述混合溶液中至pH＝10，使其沉淀完全，过夜老化12h后过滤，用去离子水洗涤3次，100℃的烘箱中干燥12h，然后在空气气氛下在马弗炉中经550℃焙烧4h，即制得铈硅复合氧化物催化剂，简记为4Ce-Si。其XRD、Raman、NH
3-SCR活性测试结果见图1-3。
Accurately weigh 6.37g of cerium ammonium nitrate and dissolve it in 150mL of ethanol, add 0.65mL of TEOS dropwise with stirring, continue stirring for 1h, then dropwise add concentrated ammonia water to the above mixed solution with stirring to pH=10, and make it precipitate Completely, aging for 12 hours overnight, filtering, washing 3 times with deionized water, drying in an oven at 100°C for 12 hours, and then calcining in a muffle furnace at 550°C for 4 hours in an air atmosphere to obtain a cerium-silicon composite oxide catalyst. Abbreviated as 4Ce-Si. The XRD, Raman, and NH 3 -SCR activity test results are shown in Figure 1-3.
实施例3：2Ce-Si催化剂的制备Example 3: Preparation of 2Ce-Si catalyst
准确称取6.37g硝酸铈铵溶于150mL乙醇中，搅拌下滴加1.30mL的TEOS，继续搅拌1h，然后在搅拌下逐滴滴加浓氨水到上述混合溶液中至pH＝10，使其沉淀完全，过夜老化12h后过滤，用去离子水洗涤3次，100℃的烘箱中干燥12h，然后在空气气氛下在马弗炉中经550℃焙烧4h，即制得铈硅复合氧化物催化剂，简记为2Ce-Si。通过X射线衍射(XRD)、拉曼光谱(Raman)、催化性能测试(NH
3-SCR反应)、抗硫中毒性能测试等表征手段来对其体相结构以及催化性能进行评价，其结果见图1-3。图1的XRD结果表明，在本发明所提及的投料浓度范围内，Ce和Si能很好地混合在一起，CeO
2的结晶程度很低，SiO
2降低了CeO
2的结晶程度。图2的Raman的结果也说明CeO
2的晶体结构被破坏，CeO
2和SiO
2之间产生了强的相互作用，氧缺陷浓度升高。图3的NH
3-SCR反应结果 表明铈硅复合氧化物催化剂的催化性能明显优于CeO
2，图中，铈硅复合氧化物NO转化率高达90％左右，其N
2选择性接近100％，随着温度增加缓慢降低，而纯CeO
2的NO转化率最高只有30％不到，其N
2选择性随着温度增加迅速降低。
Accurately weigh 6.37g of cerium ammonium nitrate and dissolve it in 150mL of ethanol, add 1.30mL of TEOS dropwise with stirring, continue stirring for 1h, and then dropwise add concentrated ammonia water to the above mixed solution with stirring to pH=10 to make it precipitate Completely, aging for 12 hours overnight, filtering, washing 3 times with deionized water, drying in an oven at 100°C for 12 hours, and then calcining in a muffle furnace at 550°C for 4 hours in an air atmosphere to obtain a cerium-silicon composite oxide catalyst. Abbreviated as 2Ce-Si. Through X-ray diffraction (XRD), Raman spectroscopy (Raman), catalytic performance test (NH 3 -SCR reaction), sulfur poisoning performance test and other characterization methods to evaluate its bulk structure and catalytic performance, the results are shown in the figure 1-3. The XRD results in Fig. 1 show that within the range of the feed concentration mentioned in the present invention, Ce and Si can be mixed together well, the degree of crystallization of CeO 2 is very low, and SiO 2 reduces the degree of crystallization of CeO 2 . The result of Raman in Fig. 2 also shows that the crystal structure of CeO 2 is destroyed, a strong interaction occurs between CeO 2 and SiO 2 and the oxygen defect concentration increases. The result of the NH 3 -SCR reaction in Figure 3 shows that the catalytic performance of the cerium-silicon composite oxide catalyst is significantly better than that of CeO 2. In the figure, the NO conversion rate of the cerium-silicon composite oxide is as high as about 90%, and its N 2 selectivity is close to 100%. The NO conversion rate of pure CeO 2 is less than 30%, and the N 2 selectivity decreases rapidly as the temperature increases.
实施例4：Ce-Si催化剂的制备Example 4: Preparation of Ce-Si catalyst
准确称取6.37g硝酸铈铵溶于150mL乙醇中，搅拌下滴加2.59mL的TEOS，继续搅拌1h，然后在搅拌下逐滴滴加浓氨水到上述混合溶液中至pH＝10，使其沉淀完全，过夜老化12h后过滤，用去离子水洗涤3次，100℃的烘箱中干燥12h，然后在空气气氛下在马弗炉中经550℃焙烧4h，即制得铈硅复合氧化物催化剂，简记为Ce-Si。其XRD、Raman、NH
3-SCR活性测试结果见图1-3。
Accurately weigh 6.37g of cerium ammonium nitrate and dissolve it in 150mL of ethanol, add 2.59mL of TEOS dropwise with stirring, continue stirring for 1h, and then dropwise add concentrated ammonia water to the above mixed solution with stirring to pH=10 to precipitate Completely, aging for 12 hours overnight, filtering, washing 3 times with deionized water, drying in an oven at 100°C for 12 hours, and then calcining in a muffle furnace at 550°C for 4 hours in an air atmosphere to obtain a cerium-silicon composite oxide catalyst. Abbreviated as Ce-Si. The XRD, Raman, and NH 3 -SCR activity test results are shown in Figure 1-3.
实施例5：Ce-2Si催化剂的制备Example 5: Preparation of Ce-2Si catalyst
准确称取6.37g硝酸铈铵溶于150ml乙醇中，搅拌下滴加5.18mL的TEOS，继续搅拌1h，然后在搅拌下逐滴滴加浓氨水到上述混合溶液中至pH＝10，使其沉淀完全，过夜老化12h后过滤，用去离子水洗涤3次，100℃的烘箱中干燥12h，然后在空气气氛下在马弗炉中经550℃焙烧4h，即制得铈硅复合氧化物催化剂，简记为Ce-2Si。通过X射线衍射(XRD)、拉曼光谱(Raman)、催化性能测试(NH
3-SCR反应)、抗硫中毒性能测试等表征手段来对其体相结构以及催化性能进行评价，其结果见图1-4。图1的XRD结果表明，在本发明所提及的投料浓度范围内，Ce和Si能很好地混合在一起，当Ce与Si的摩尔比小于等于1：2时，CeO
2的结晶程度很低，SiO
2降低了CeO
2的结晶程度。图2的Raman的结果也说明CeO
2的晶体结构被破坏，CeO
2和SiO
2之间产生了强的相互作用，氧缺陷浓度升高。图3的NH
3-SCR反应结果表明铈硅复合氧化物催化剂的催化性能明显优于CeO
2，图中，铈硅复合氧化物NO转化率高达90％左右，其N
2选择性接近100％，随着温度增加缓慢降低，而纯CeO
2的NO转化率最高只有30％不到，其N
2选择性随着温度增加迅速降低。图4中显示，铈硅复合氧化物在250℃表现出优异的抗硫中毒性能，NO转化率长时间稳定在90％以上，没有明显下降趋势，而CeO
2的NO转化率下降严重，表现出明显的硫中毒特点。
Accurately weigh 6.37g cerium ammonium nitrate and dissolve it in 150ml ethanol, add 5.18mL TEOS dropwise with stirring, continue stirring for 1h, then dropwise add concentrated ammonia water dropwise with stirring to the above mixed solution to pH=10, and make it precipitate Completely, aging for 12 hours overnight, filtering, washing 3 times with deionized water, drying in an oven at 100°C for 12 hours, and then calcining in a muffle furnace at 550°C for 4 hours in an air atmosphere to obtain a cerium-silicon composite oxide catalyst. Abbreviated as Ce-2Si. Through X-ray diffraction (XRD), Raman spectroscopy (Raman), catalytic performance test (NH 3 -SCR reaction), sulfur poisoning performance test and other characterization methods to evaluate its bulk structure and catalytic performance, the results are shown in the figure 1-4. The XRD results in Figure 1 show that Ce and Si can be mixed together well within the feeding concentration range mentioned in the present invention. When the molar ratio of Ce to Si is less than or equal to 1:2, the degree of crystallization of CeO 2 is very high. Low, SiO 2 reduces the crystallinity of CeO 2 . The result of Raman in Fig. 2 also shows that the crystal structure of CeO 2 is destroyed, a strong interaction occurs between CeO 2 and SiO 2 and the oxygen defect concentration increases. The results of the NH 3 -SCR reaction in Figure 3 show that the catalytic performance of the cerium-silicon composite oxide catalyst is significantly better than that of CeO 2. In the figure, the NO conversion rate of the cerium-silicon composite oxide is as high as about 90%, and its N 2 selectivity is close to 100%. The NO conversion rate of pure CeO 2 is less than 30%, and the N 2 selectivity decreases rapidly as the temperature increases. Figure 4 shows that the cerium-silicon composite oxide exhibits excellent sulfur poisoning resistance at 250°C, and the NO conversion rate has been stable above 90% for a long time without a significant downward trend. However, the NO conversion rate of CeO 2 has dropped seriously, showing Obvious characteristics of sulfur poisoning.
实施例6：Ce-4Si催化剂的制备Example 6: Preparation of Ce-4Si catalyst
准确称取6.37g硝酸铈铵溶于150ml乙醇中，搅拌下滴加10.36mL的TEOS，继续搅拌1h，然后在搅拌下逐滴滴加浓氨水到上述混合溶液中至pH＝10，使其沉淀完全，过夜老化12h后过滤，用去离子水洗涤3次，100℃的烘箱中干燥12 h，然后在空气气氛下在马弗炉中经550℃焙烧4h，即制得铈硅复合氧化物催化剂，简记为Ce-4Si。其XRD、Raman、NH
3-SCR活性测试结果见图1-3。
Accurately weigh 6.37g of cerium ammonium nitrate and dissolve it in 150ml of ethanol, add 10.36mL of TEOS dropwise with stirring, continue stirring for 1h, and then dropwise add concentrated ammonia water to the above mixed solution with stirring to pH=10 to precipitate Completely, aging for 12 hours overnight, filtering, washing 3 times with deionized water, drying in an oven at 100°C for 12 hours, and calcining in a muffle furnace at 550°C for 4 hours under air atmosphere to obtain a cerium-silicon composite oxide catalyst , Abbreviated as Ce-4Si. The XRD, Raman, and NH 3 -SCR activity test results are shown in Figure 1-3.
实施例7：铈硅复合氧化物脱硝催化性能测定Example 7: Determination of catalytic performance of cerium-silicon composite oxide for denitration
将制备的铈硅复合氧化物催化剂应用于NH
3-SCR反应，具体反应条件如下：催化反应测试在固定床连续流动石英反应器中进行。催化剂粒度为60-80目，用量为250mg。反应气体组成为：500ppm NO，500ppm NH
3，200ppm SO
2，5％O
2，N
2作平衡气，反应中的气体空速为30000mL·g
-1·h
-1。在反应前，催化剂需用高纯N
2在200℃下吹扫1h。催化反应在50-450℃进行，活性数据在反应达到平衡后采集。产物由Thermofisher IS10 FTIR检测分析，NO转化率和N
2选择性通过以下公式计算：
The prepared cerium-silicon composite oxide catalyst was applied to the NH 3 -SCR reaction, and the specific reaction conditions were as follows: the catalytic reaction test was carried out in a fixed-bed continuous flow quartz reactor. The particle size of the catalyst is 60-80 mesh, and the dosage is 250 mg. The reaction gas composition is: 500 ppm NO, 500 ppm NH 3 , 200 ppm SO 2 , 5% O 2 , and N 2 as the balance gas, and the gas space velocity in the reaction is 30000 mL·g -1 ·h -1 . Before the reaction, the catalyst needs to be purged with high purity N 2 at 200°C for 1 h. The catalytic reaction is carried out at 50-450°C, and the activity data is collected after the reaction reaches equilibrium. The product was detected and analyzed by Thermofisher IS10 FTIR, and the NO conversion rate and N 2 selectivity were calculated by the following formula:
其结果见附图3，铈硅复合氧化物Ce-2Si表现出很好的催化性能(NO转化率，N
2选择性和抗硫中毒能力)，结果表明铈硅复合氧化物催化剂具有优越的催化性能，NO转化率和N
2选择性均高于纯CeO
2；
The results are shown in Figure 3. The cerium-silicon composite oxide Ce-2Si exhibits very good catalytic performance (NO conversion rate, N 2 selectivity and sulfur poisoning resistance). The results show that the cerium-silicon composite oxide catalyst has excellent catalytic performance. Performance, NO conversion rate and N 2 selectivity are higher than pure CeO 2 ;
Claims (10)
- 一种铈硅复合氧化物的制备方法，其特征在于，包括如下步骤：A preparation method of cerium-silicon composite oxide is characterized in that it comprises the following steps:1)将硝酸铈铵溶于乙醇，得到的硝酸铈铵乙醇溶液，在搅拌下滴加正硅酸四乙酯，得到混合溶液，所述混合溶液中的硝酸铈铵和正硅酸四乙酯的摩尔比为4∶1-1∶4，继续搅拌；1) Dissolve cerium ammonium nitrate in ethanol to obtain an ethanol solution of cerium ammonium nitrate, add tetraethyl orthosilicate dropwise with stirring to obtain a mixed solution, the mixed solution of cerium ammonium nitrate and tetraethyl orthosilicate The molar ratio is 4:1-1:4, continue to stir;2)步骤1)所得混合溶液在搅拌下滴加浓氨水，产生沉淀，老化沉淀；2) Step 1) Add concentrated ammonia water dropwise to the resulting mixed solution under stirring to cause precipitation and aging precipitation;3)步骤2)所得沉淀经过过滤，洗涤，干燥，焙烧，得到铈硅复合氧化物。3) Step 2) The obtained precipitate is filtered, washed, dried and calcined to obtain a cerium-silicon composite oxide.
- 根据权利要求1所述的铈硅复合氧化物的制备方法，其特征在于，步骤1)中所述硝酸铈铵乙醇溶液，其浓度为0.005mol/L～0.2mol/L。The method for preparing a cerium-silicon composite oxide according to claim 1, wherein the concentration of the ethanol solution of cerium ammonium nitrate in step 1) is 0.005 mol/L to 0.2 mol/L.
- 根据权利要求1所述的铈硅复合氧化物的制备方法，其特征在于，步骤1)中所述继续搅拌的时长为1h。The method for preparing a cerium-silicon composite oxide according to claim 1, wherein the duration of the continued stirring in step 1) is 1 h.
- 根据权利要求1所述的铈硅复合氧化物的制备方法，其特征在于，步骤2)中所述滴加浓氨水至所述混合溶液的pH＝10时停止，所述浓氨水的浓度为13.2mol/L。The method for preparing a cerium-silicon composite oxide according to claim 1, wherein in step 2), the dropwise addition of concentrated ammonia is stopped when the pH of the mixed solution is 10, and the concentration of the concentrated ammonia is 13.2 mol/L.
- 根据权利要求1所述的铈硅复合氧化物的制备方法，其特征在于，步骤2)中所述老化沉淀的时间为12h。The method for preparing a cerium-silicon composite oxide according to claim 1, wherein the time of the aging precipitation in step 2) is 12 hours.
- 根据权利要求1所述的铈硅复合氧化物的制备方法，其特征在于，步骤3)中所述洗涤是用去离子水洗涤3次，所述干燥是在100℃的烘箱中干燥12h。The method for preparing a cerium-silicon composite oxide according to claim 1, wherein the washing in step 3) is washing with deionized water three times, and the drying is drying in an oven at 100° C. for 12 hours.
- 根据权利要求1所述的铈硅复合氧化物的制备方法，其特征在于，步骤3)中所述焙烧是在马弗炉中，温度为550℃，时长4h。The method for preparing a cerium-silicon composite oxide according to claim 1, wherein the firing in step 3) is in a muffle furnace at a temperature of 550° C. and a duration of 4 hours.
- 权利要求1-7所述的铈硅复合氧化物的制备方法得到的铈硅复合氧化物。A cerium-silicon composite oxide obtained by the method of preparing a cerium-silicon composite oxide according to claims 1-7.
- 根据权利要求8所述的铈硅复合氧化物，其特征在于，所述的铈硅复合氧化物为Ce-2Si。9. The cerium-silicon composite oxide of claim 8, wherein the cerium-silicon composite oxide is Ce-2Si.
- 权利要求8所述的铈硅复合氧化物作为烟气脱硝催化剂的应用。Application of the cerium-silicon composite oxide of claim 8 as a flue gas denitration catalyst.
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