CN112844404A - Low-temperature denitration catalyst with TiO2 nanotube as carrier and preparation and application thereof - Google Patents

Low-temperature denitration catalyst with TiO2 nanotube as carrier and preparation and application thereof Download PDF

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CN112844404A
CN112844404A CN202110122576.5A CN202110122576A CN112844404A CN 112844404 A CN112844404 A CN 112844404A CN 202110122576 A CN202110122576 A CN 202110122576A CN 112844404 A CN112844404 A CN 112844404A
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nanotube
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张向辉
王蕾
赵安民
蔡洪城
黄晨
贺安平
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Southwest Research and Desigin Institute of Chemical Industry
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention provides a method for preparing a titanium dioxide (TiO)2A low-temperature denitration catalyst with a nanotube as a carrier belongs to the technical field of denitration catalysts. The catalyst is made of TiO2Nanotube as carrier and supported MnOx、CeO2、Fe2O3The weight percentage of each component is as follows: MnOx：3.0‑15％，CeO2：2.0‑12％，Fe2O3：3.0‑15％，TiO2Nanotube: 58 to 90 percent. The invention also provides a preparation method and application of the catalyst. Support TiO2The rich hydrogen protons in the nanotube can perform ion exchange with alkali metal ions, so that the alkali metal ions are fixed in the multilayer tube wall of the nanotube to protect active components from being affected, thereby improving the alkali metal poisoning resistance of the catalyst. MnO ofx、CeO2、Fe2O3Supported on TiO with high specific surface area2The higher specific surface area of the nanotube surface effectively promotes the dispersion of each component on the surface of the carrier, and reduces SO in the flue gas2Oxidation rate of (C), reduction of metal sulfate and (NH)4)HSO4The amount of the catalyst produced improves the sulfur poisoning resistance of the catalyst.

Description

Low-temperature denitration catalyst with TiO2 nanotube as carrier and preparation and application thereof
Technical Field
The invention belongs to the technical field of denitration catalysts, and particularly relates to a catalyst prepared from TiO2A low-temperature denitration catalyst with a nano tube as a carrier, and preparation and application thereof.
Background
Nitrogen Oxides (NO)x) Is one of the main atmospheric pollutants and one of the main causes of haze formation. By NH3Selective catalytic reduction denitration technology (SCR technology) for reducing agent is to control NOxContamination is the most mature and effective technique. The first SCR denitration technology adopted is in the power industry, and NO is caused in the power industryxThe total amount of emissions once exceeded 60% of the total amount, which was the largest in the total amount of demand for the denitration catalyst. Meanwhile, the flue gas emission temperature in the power industry is high, the denitration effect of the SCR technology is good, and the SCR denitration technology is developed in the power industry to the greatest extent. At present, most of electric power enterprises in China have already finished denitration reformation, and SCR denitration technology is adopted for more than 90 percent of the electric power enterprises in China. But for other heavy pollution industries, such as: refining, coking, ceramics, glass, cement, etc., NO thereofxThe emission amount accounts for 30-40% of the total amount, and because the temperature of the emitted flue gas is low, SO may exist at the same time2High content of H2The content of O is high, the content of dust is high, the difficult problems of toxic substances such as tar, naphthalene, mercury, arsenic and the like are accompanied, the difficulty of the integral denitration technology is high, and the conventional SCR denitration technology cannot meet the emission requirement. With the development of the desulfurization and denitrification technical level in recent years, breakthroughs are made in the aspects of catalysts and process technology, and the low-temperature flue gas denitrification modification engineering of the industries is actively promoted in recent years.
Disclosure of Invention
The invention aims to provide a method for preparing a titanium dioxide (TiO)2A low-temperature denitration catalyst with a nano tube as a carrier, and preparation and application thereof. The invention uses strong alkaline hydrothermal method to prepare nano-tubular titanium dioxide with high specific surface area and ordered pore structure as carrier, andMnOx and CeO are deposited and precipitated2、Fe2O3The catalyst is uniformly loaded on the surface of a carrier, the structure of the catalyst is improved, the catalytic activity and the anti-poisoning capability of the catalyst are improved, and the NOx in the industrial flue gas can be efficiently removed at a lower temperature.
The purpose of the invention is realized by the following technical scheme:
by TiO2Low-temperature denitration catalyst with nanotube as carrier, wherein the catalyst is TiO2Nanotube as carrier and supported MnOx、CeO2、Fe2O3The weight percentage of each component is as follows: MnOx：3.0-15％，CeO2：2.0-12％，Fe2O3：3.0-15％，TiO2Nanotube: 58 to 90 percent.
Further, the MnO is calculated by mass percentxThe mass content of (b) is preferably 5.0 to 12%, more preferably 7.0 to 10%; the CeO2The mass content of (b) is preferably 5 to 10%, more preferably 7 to 8%; said Fe2O3The mass content is preferably 4.0 to 12%, and more preferably 6 to 8%; the TiO is2The mass content of the nanotube is preferably 60 to 80%, and more preferably 65 to 75%.
TiO2The nano tube has the advantages of good thermal stability, strong mechanical strength, high sulfur resistance and the like, and has larger specific surface area and pore volume due to the special hollow tubular structure and highly ordered pore channels, thereby showing unique adsorption capacity. Preparation of TiO by strong alkaline hydrothermal method2Nanotube of TiO2The surface has larger specific surface area, thereby improving the dispersibility of active components of the low-temperature denitration catalyst and further increasing the catalytic activity of the catalyst.
Oxide of Mn (MnO)x) Contains a large amount of free O, promotes good circulation in the catalytic reaction, and is due to Mn4+Has an electron orbit of d3，Mn2+Has an electron orbit of d5The catalyst is easy to migrate to ammonia gas and oxygen gas to promote the oxidation-reduction reaction, so that the catalyst has excellent low-temperature catalytic activity. Prepared by doping cerium and manganeseThe composite catalyst can effectively improve the low-temperature activity of the catalyst, and the doping of Ce can greatly improve MnOx-TiO2The Ce doping increases the specific surface area of the catalyst, and improves Mn with better catalytic activity4+The concentration of (c). Mn doping can change CeO2The lattice structure of (2) generates a large number of oxygen vacancies, promoting the improvement of redox ability. Fe2O3Can improve the Mn on the surface of the catalyst4+The amount and the dispersion degree of the catalyst can effectively improve the activity of the catalyst and can also effectively enhance the water poisoning resistance of the catalyst.
Further, the catalyst is TiO prepared by a strong alkali hydrothermal method2The nano-tube is taken as a carrier, and the component MnO is deposited and precipitatedx、CeO2、Fe2O3Loaded on the surface of a carrier, and further dried and roasted to obtain the catalyst.
Further, the TiO2The length of the nanotube is 60-250nm, the outer diameter is 6-20nm, the wall thickness is 2-8nm, the specific surface area is 160-280m2/g。
By TiO2The preparation method of the low-temperature denitration catalyst with the nanotube as the carrier comprises the following steps:
1) adding TiO into the mixture2Adding NaOH solution into the particles, carrying out ultrasonic oscillation, mechanically stirring until the particles are uniformly mixed, transferring the uniformly mixed suspension into a tetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal reaction at high temperature, and naturally cooling to room temperature;
2) washing a white particle product generated by a hydrothermal reaction with deionized water, then washing with a dilute HCl solution, washing to neutrality with the deionized water, filtering, drying to obtain a nanotube-shaped titanium material, and finally roasting to obtain TiO2A nanotube;
3) adding TiO into the mixture2Nanotube incorporation of Mn (NO)3)2、Ce(NO3)3、Fe(NO3)3Stirring the mixed solution at constant temperature, and dripping CO (NH) into the mixed solution while stirring2)2And (3) carrying out deposition-precipitation on the solution to obtain a precipitate, washing the precipitate to be neutral, drying and roasting to obtain a catalyst finished product.
Further, the concentration of the NaOH solution is 6-15 mol/L; the TiO is2The particles are P25 nano TiO2Average particle diameter of 10-30nm and specific surface area of 40-120m2(ii)/g; the TiO is2The mass ratio of the particles to NaOH is 1: 15-80.
Further, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 6-48 h.
Further, in the step 2), the concentration of the dilute HCl solution is 0.03-0.30mol/L, the dilute HCl solution is washed by HCl solution until the pH value is less than or equal to 1, and then the dilute HCl solution is washed by deionized water until the dilute HCl solution is neutral; the drying temperature is 105-120 ℃, and the time is 4-24 h; the roasting temperature is 250-400 ℃, and the time is 2-8 h.
Further, in the step 3), the temperature of the mixed solution is 50-85 ℃; the CO (NH)2)2The mass concentration of the solution is 5-20%, and CO (NH)2)2Dropwise adding the solution until metal ions are completely precipitated; the drying temperature is 105-120 ℃, and the time is 4-24 h; the roasting temperature is 250-500 ℃, and the time is 2-8 h.
By TiO2Application of low-temperature denitration catalyst with nanotube as carrier in low-temperature removal of NO in flue gasxThe use of (1).
Compared with the prior art, the invention has the following beneficial effects:
1. MnO ofx、CeO2、Fe2O3Supported on TiO with high specific surface area2The higher specific surface area of the nanotube surface effectively promotes the dispersion of each component on the surface of the carrier, and reduces SO in the flue gas2Oxidation rate of (C), reduction of metal sulfate and (NH)4)HSO4The amount of the catalyst produced improves the sulfur poisoning resistance of the catalyst.
2. Acidification of TiO with HCl solution2Nanotube treatment, not only to ensure TiO2The completeness of the nanotube structure also increases the surface acid position, enhances the surface adsorption capacity of the catalyst, promotes the content of oxygen chemically adsorbed on the surface of the catalyst, promotes the oxidation-reduction reaction, and improves the denitration efficiency of the catalyst under the low-temperature condition.
3. Support TiO2The rich hydrogen protons in the nanotube can perform ion exchange with alkali metal ions, so that the alkali metal ions are fixed in the multilayer tube wall of the nanotube, active components are protected from being affected, and the alkali metal poisoning resistance of the catalyst is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, "%" is used in mass% unless otherwise specified.
Example 1
This example uses TiO2The specific preparation process of the low-temperature denitration catalyst with the nanotube as the carrier is as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, carrying out ultrasonic oscillation for 30min, mechanically stirring for 60min until the particles are uniformly mixed, transferring the suspension into a 300ml polytetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal treatment for 24h at the temperature of 160 ℃, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
Weigh 0.54gMn (NO)3)2、0.41gCe(NO3)3、0.32gFe(NO3)3And 50ml of deionized water to prepare a mixed solution, and mixing 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; washing the precipitate with deionized water to neutrality at 120 deg.CDrying for 12h at the temperature, and roasting for 6h at the temperature of 300 ℃ to obtain the catalyst A.
In the catalyst a of this example, the mass percentages of the components are: MnOx：10.15％，CeO2：8.37％，Fe2O3：4.09％，TiO2：77.39％。
Example 2
This example uses TiO2The specific preparation process of the low-temperature denitration catalyst with the nanotube as the carrier is as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, carrying out ultrasonic oscillation for 30min, mechanically stirring for 60min until the particles are uniformly mixed, transferring the suspension into a 300ml polytetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal treatment for 24h at the temperature of 160 ℃, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
Weigh 0.52gMn (NO)3)2、0.20gCe(NO3)3、0.31gFe(NO3)3And 50ml of deionized water to prepare a mixed solution, and mixing 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the catalyst B.
In the catalyst B of this example, the mass percentages of the components are: MnOx：10.27％，CeO2：4.29％，Fe2O3：4.16％，TiO2：81.29％。
Example 3
This example uses TiO2The specific preparation process of the low-temperature denitration catalyst with the nanotube as the carrier is as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, carrying out ultrasonic oscillation for 30min, mechanically stirring for 60min until the particles are uniformly mixed, transferring the suspension into a 300ml polytetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal treatment for 24h at the temperature of 160 ℃, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
0.31g Mn (NO) is weighed3)2、0.39g Ce(NO3)3、0.31g Fe(NO3)3And 50ml of deionized water to prepare a mixed solution, and 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the catalyst C.
In the catalyst C of this example, the mass percentages of the components are: MnOx：6.13％，CeO2：8.37％，Fe2O3：4.16％，TiO2：81.35％。
Example 4
This example uses TiO2The specific preparation process of the low-temperature denitration catalyst with the nanotube as the carrier is as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, ultrasonically oscillating for 30min, mechanically stirring for 60min to mix uniformly, transferring the suspension into a 300ml stainless steel hydrothermal kettle with polytetrafluoroethylene lining, and performing hydrothermal treatment at 160 deg.CAfter conditioning for 24 hours, naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
Weigh 0.58gMn (NO)3)2、0.43gCe(NO3)3、0.73gFe(NO3)3And 50ml of deionized water to prepare a mixed solution, and mixing 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the catalyst D.
In the catalyst D of this example, the mass percentages of the components are: MnOx：10.25％，CeO2：8.25％，Fe2O3：8.76％，TiO2：72.74％。
Comparative example 1
The specific preparation procedure for the catalyst of this comparative example was as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, carrying out ultrasonic oscillation for 30min, mechanically stirring for 60min until the particles are uniformly mixed, transferring the suspension into a 300ml polytetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal treatment for 24h at the temperature of 160 ℃, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
Weigh 0.37gCe (NO)3)3、0.57gFe(NO3)3And 50ml of deionized water to prepare a mixed solution, and mixing 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the catalyst E.
In the catalyst E of the comparative example, the mass percentages of the components are as follows: MnOx：0％，CeO2：8.19％，Fe2O3：7.89％，TiO2：83.92％。
Comparative example 2
The specific preparation procedure for the catalyst of this comparative example was as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, carrying out ultrasonic oscillation for 30min, mechanically stirring for 60min until the particles are uniformly mixed, transferring the suspension into a 300ml polytetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal treatment for 24h at the temperature of 160 ℃, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
Weigh 0.51gMn (NO)3)2、0.61gFe(NO3)3And 50ml of deionized water to prepare a mixed solution, and 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the catalyst F.
In the catalyst F of the comparative example, the mass percentages of the components are as follows: MnOx：10.12％，CeO2：0％，Fe2O3：8.22％，TiO2：81.66％。
Comparative example 3
The specific preparation procedure for the catalyst of this comparative example was as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, carrying out ultrasonic oscillation for 30min, mechanically stirring for 60min until the particles are uniformly mixed, transferring the suspension into a 300ml polytetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal treatment for 24h at the temperature of 160 ℃, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
0.52g Mn (NO) was weighed3)2、0.41g Ce(NO3)3And 50ml of deionized water to prepare a mixed solution, and 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the catalyst G.
In the catalyst G of the comparative example, the mass percentages of the components are as follows: MnOx：10.23％，CeO2：8.76％，Fe2O3：0％，TiO2：81.01％。
Comparative example 4
The specific preparation procedure for the catalyst of this comparative example was as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the granules, and performing ultrasonic treatmentAfter oscillating for 30min, mechanically stirring for 60min until the mixture is uniform, transferring the suspension into a 300ml stainless steel hydrothermal kettle with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 160 ℃ for 24h, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, and then using 0.20mol/L HNO3Washing the solution until the pH value is less than or equal to 1, washing the solution to be neutral by using deionized water, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nano tubular sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
Weigh 0.54gMn (NO)3)2、0.41gCe(NO3)3、0.32gFe(NO3)3And 50ml of deionized water to prepare a mixed solution, and 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12H, and roasting at 300 ℃ for 6H to obtain the catalyst H.
In the catalyst H of the comparative example, the mass percentages of the components are as follows: MnOx：10.15％，CeO2：8.37％，Fe2O3：4.09％，TiO2：77.39％。
Comparative example 5
The specific preparation procedure for the catalyst of this comparative example was as follows:
weigh 0.54gMn (NO)3)2、0.41gCe(NO3)3、0.32g Fe(NO3)3And 50ml of deionized water are prepared into a mixed solution, and 2.0g of P25 type TiO is added2Adding the granules into the mixed solution, and stirring for 1h at the constant temperature of 75 ℃; adding CO (NH) with the mass concentration of 10% dropwise into the mixed solution2)2The solution is deposited and precipitated, and is dripped until the pH value of the mixed solution is more than or equal to 10.0; and washing the precipitate with deionized water to neutrality, drying at 120 ℃ for 12h, and roasting at 300 ℃ for 6h to obtain the catalyst I.
In the catalyst H of the comparative example, the mass percentages of the components are as follows: MnOx：10.15％，CeO2：8.37％，Fe2O3：4.09％，TiO2：77.39％。
Comparative example 6
The specific preparation procedure for the catalyst of this comparative example was as follows:
200ml of a 10mol/L NaOH solution was prepared, and 2.5g of TiO 25 type P2Adding NaOH solution into the particles, carrying out ultrasonic oscillation for 30min, mechanically stirring for 60min until the particles are uniformly mixed, transferring the suspension into a 300ml polytetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal treatment for 24h at the temperature of 160 ℃, and naturally cooling to room temperature.
Washing a sodium titanate white particle product generated by a hydrothermal reaction with deionized water, then washing with 0.20mol/L HCl solution until the pH value is less than or equal to 1, washing with deionized water to be neutral, filtering, and drying a filter cake at 120 ℃ for 12h to obtain a nanotube-shaped sodium titanate nano material; roasting the sodium titanate nano material in a muffle furnace at the temperature of 300 ℃ for 4h to obtain TiO2A nanotube.
Weigh 0.54gMn (NO)3)2、0.41gCe(NO3)3、0.32gFe(NO3)3And 50ml of deionized water to prepare a mixed solution, and mixing 2.0g of TiO2Adding the nanotube into the mixed solution, and stirring at the constant temperature of 75 ℃ to dip for 1 h; and centrifuging the impregnated particles, washing the particles to be neutral by using deionized water, drying the particles for 12 hours at the temperature of 120 ℃, and roasting the particles for 6 hours at the temperature of 300 ℃ to obtain the catalyst J.
In the catalyst J of the comparative example, the mass percentages of the components are as follows: MnOx：10.15％，CeO2：8.37％，Fe2O3：4.09％，TiO2：77.39％。
And (3) activity test:
the prepared catalysts of examples and comparative examples were loaded into a stainless steel reaction tube for low-temperature denitration activity test, the catalyst loading was 4.0g (. about.4.8 ml), the reaction temperature: and (3) 90-240 ℃, reaction space velocity: 15000h-1(ii) a Concentration of NO in flue gas: 1200mg/Nm3；NH3Concentration: 1200mg/Nm3，O2Volume concentration: 8 percent; h2O volume concentration: 15 percent; the rest is N2。
The formula for the calculation of the NO conversion is as follows:
Figure BDA0002922608780000121
wherein: etaNOIs the NO conversion; c. CNO inletIs the NO inlet concentration; c. CNO outletIs the NO outlet concentration;
the low-temperature denitration activity test results of the catalyst are shown in the following table 1:
table 1 test results of low-temperature denitration activity of catalysts prepared in examples and comparative examples
Figure BDA0002922608780000122
As can be seen from the above table, examples 1-4 all have good denitration effects at a temperature range of 90-240 ℃, and examples 1-4 have significantly improved denitration efficiency compared with comparative examples 1-6, which indicates that TiO is used2MnO is loaded by using nano tube as carrier through deposition-precipitation methodx、CeO2、Fe2O3The denitration efficiency of the catalyst can be obviously improved.
Comparative examples 1 to 3 illustrate MnOxIs the main active component, CeO2、Fe2O3The active assistant can effectively improve the performance of the catalyst and is indispensable for keeping the high denitration efficiency of the catalyst; comparative example 4 demonstrates that hydrochloric acid is more effective at displacing Na from hydrothermal reaction than other acids+The prepared catalyst has higher activity, and the denitration effect of the catalyst is improved; comparative example 5 illustrates TiO2Nanotube to TiO2The particles have higher denitration efficiency; comparative example 6 illustrates that the deposition-precipitation method for supporting the active component can improve the denitration effect of the catalyst compared with the conventional impregnation method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. By TiO2The low-temperature denitration catalyst with the nanotube as the carrier is characterized in that the catalyst is TiO2Nanotube as carrier and supported MnOx、CeO2、Fe2O3The weight percentage of each component is as follows: MnOx：3.0-15％，CeO2：2.0-12％，Fe2O3：3.0-15％，TiO2Nanotube: 58 to 90 percent.
2. The method of claim 1, wherein the compound is TiO2The low-temperature denitration catalyst with the nanotube as the carrier is characterized in that the catalyst is TiO prepared by a strong alkaline hydrothermal method2The nano-tube is taken as a carrier, and the component MnO is deposited and precipitatedx、CeO2、Fe2O3Loaded on the surface of a carrier, and further dried and roasted to obtain the catalyst.
3. The method of claim 1, wherein the compound is TiO2The low-temperature denitration catalyst with the nano tube as the carrier is characterized in that the TiO is2The length of the nanotube is 60-250nm, the outer diameter is 6-20nm, the wall thickness is 2-8nm, the specific surface area is 160-280m2/g。
4. A TiO compound according to any one of claims 1 to 32The preparation method of the low-temperature denitration catalyst with the nanotube as the carrier is characterized by comprising the following steps of:
1) adding TiO into the mixture2Adding NaOH solution into the particles, carrying out ultrasonic oscillation, mechanically stirring until the particles are uniformly mixed, transferring the uniformly mixed suspension into a tetrafluoroethylene-lined stainless steel hydrothermal kettle, carrying out hydrothermal reaction at high temperature, and naturally cooling to room temperature;
2) white granular products generated by the hydrothermal reaction are firstly washed by deionized water and then are usedWashing with dilute HCl solution, washing with deionized water to neutrality, filtering, drying to obtain tubular titanium material, and roasting to obtain TiO2A nanotube;
3) adding TiO into the mixture2Nanotube incorporation of Mn (NO)3)2、Ce(NO3)3、Fe(NO3)3Stirring the mixed solution at constant temperature, and dripping CO (NH) into the mixed solution while stirring2)2And (3) carrying out deposition-precipitation on the solution to obtain a precipitate, washing the precipitate to be neutral, drying and roasting to obtain a catalyst finished product.
5. A process according to claim 4, wherein the compound is TiO2The preparation method of the low-temperature denitration catalyst with the nanotube as the carrier is characterized in that the concentration of the NaOH solution is 6-15 mol/L; the TiO is2The particles are P25 nano TiO2Average particle diameter of 10-30nm and specific surface area of 40-120m2(ii)/g; the TiO is2The mass ratio of the particles to NaOH is 1: 15-80.
6. A process according to claim 4, wherein the compound is TiO2The preparation method of the low-temperature denitration catalyst with the nanotube as the carrier is characterized in that the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 6-48 h.
7. A process according to claim 4, wherein the compound is TiO2The preparation method of the low-temperature denitration catalyst with the nanotube as the carrier is characterized in that in the step 2), the concentration of the dilute HCl solution is 0.03-0.30mol/L, the dilute HCl solution is used for cleaning until the pH value is less than or equal to 1, and then the dilute HCl solution is cleaned to be neutral by deionized water; the drying temperature is 105-120 ℃, and the time is 4-24 h; the roasting temperature is 250-400 ℃, and the time is 2-8 h.
8. A process according to claim 4, wherein the compound is TiO2The preparation method of the low-temperature denitration catalyst with the nanotube as the carrier is characterized in that in the step 3), the temperature of the mixed solution is 50-85 ℃; the CO (NH)2)2The mass concentration of the solution is 5-20%, and CO (NH)2)2The solution is added dropwise to the metalCompletely precipitating ions; the drying temperature is 105-120 ℃, and the time is 4-24 h; the roasting temperature is 250-500 ℃, and the time is 2-8 h.
9. A TiO compound according to any one of claims 1 to 32The application of the low-temperature denitration catalyst with the nanotube as the carrier is characterized in that the catalyst is used for removing NO in flue gas at low temperaturexThe use of (1).
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