阅读说明：本技术 一种制备CuSO4/TiO2抗硫脱硝催化剂的方法 (Preparation of CuSO4/TiO2Method for preparing sulfur-resistant denitration catalyst ) 是由 于艳科 田明姣 姜泽宇 建艳飞 何炽 于 2020-05-22 设计创作，主要内容包括：本发明公开了一种制备CuSO<Sub>4</Sub>/TiO<Sub>2</Sub>抗硫脱硝催化剂的方法,将钛酸丁酯溶于无水乙醇中,得到钛酸丁酯溶液；将CuSO<Sub>4</Sub>·5H<Sub>2</Sub>O溶于乙醇和水的混合液中,得到CuSO<Sub>4</Sub>溶液；搅拌条件下,将钛酸丁酯溶液加入到CuSO<Sub>4</Sub>溶液中,得到溶胶；将溶胶静置老化后,得到凝胶；将凝胶烘干后,经焙烧得到CuSO<Sub>4</Sub>/TiO<Sub>2</Sub>催化剂。该发明制备的CuSO<Sub>4</Sub>/TiO<Sub>2</Sub>催化剂具有较大的比表面积和较多的酸性位数目,在280～380℃之间显示出高于90％的脱硝效率,并且烟气中SO<Sub>2</Sub>对催化剂活性未有明显影响,克服了非钒基脱硝催化剂抗硫性能低的缺点。本发明合成方法简单,原材料价格低廉,适合大规模的工业化生产。(The invention discloses a method for preparing CuSO 4 /TiO 2 Dissolving butyl titanate in absolute ethyl alcohol to obtain a butyl titanate solution; mixing CuSO 4 ·5H 2 Dissolving O in the mixed solution of ethanol and water to obtain CuSO 4 A solution; adding the butyl titanate solution into CuSO under the stirring condition 4 Obtaining sol in the solution; standing and aging the sol to obtain gel; drying the gel, and roasting to obtain CuSO 4 /TiO 2 A catalyst. The CuSO prepared by the invention 4 /TiO 2 The catalyst has larger specific surface area and more acid sites, and shows higher than that at the temperature of 280-380 DEG CDenitration efficiency of 90 percent and SO in flue gas 2 Has no obvious influence on the activity of the catalyst, and overcomes the defect of low sulfur resistance of the non-vanadium-based denitration catalyst. The synthetic method is simple, the raw materials are low in price, and the method is suitable for large-scale industrial production.)

1. Preparation of CuSO₄/TiO₂The method for preparing the sulfur-resistant denitration catalyst is characterized by comprising the following specific steps of:

(1) dissolving butyl titanate in absolute ethyl alcohol to obtain a butyl titanate solution; mixing CuSO₄·5H₂Dissolving O in the mixed solution of water and ethanol to obtain CuSO₄A solution; the concentration of the butyl titanate is 0.2-2 mol/L; CuSO₄The concentration of (A) is 0.02-0.2 mol/L; butyl titanate and CuSO₄The molar ratio of (A) to (B) is 80: 1-8: 1;

(2) adding the butyl titanate solution in the step (1) into CuSO under the stirring condition₄Obtaining sol in the solution; stirring at 200-1000 r/min and at room temperature;

(3) standing and aging the sol obtained in the step (2) for 2-6 h to obtain gel;

(4) drying the gel obtained in the step (3), and roasting to obtain CuSO₄/TiO₂The drying temperature of the catalyst is 100-130 ℃; the roasting temperature is 450-600 ℃, and the heating rate is 2-5 ℃/min.

2. A method of making CuSO according to claim 1₄/TiO₂The method for preparing the sulfur-resistant denitration catalyst is characterized by comprising the following steps: the volume ratio of water to ethanol in the mixed solution of water and ethanol in the step (1) is 0.2: 1-4: 1.

Technical Field

The invention belongs to the technical field of air pollution treatment, and particularly relates to CuSO₄/TiO₂A method for synthesizing a high-sulfur-resistance denitration catalyst.

Background

Nitrogen Oxides (NO) produced by combustion of fossil fuels_xMainly containing NO and NO₂) Is one of the main atmospheric pollutants in China at present, and can cause environmental problems such as acid rain, photochemical smog, dust haze and the like. Rapid and effective reduction of NO_xThe discharge of the waste water is one of important ways for improving the atmospheric environment in China. Selective catalytic reduction of ammonia (NH)₃-SCR) is the mainstream flue gas denitration method at present and is applied to thermal power plants, iron and steel plants, cement plants and other fixed source NO on a large scale_xIn the row reduction. The method utilizes ammonia gas and NO_xThe reaction generates pollution-free nitrogen and water, thereby achieving the purpose of removing NO_xThe purpose of (1). The denitration catalyst is one of the core technologies of the method and is directly related to the method for NO_xThe removal efficiency of (1). Commercial denitration catalyst V in use at present₂O₅-WO₃/TiO₂Middle V₂O₅Has high biological toxicity, easily produces adverse effect on the environment and easily removes SO in the flue gas₂By oxidation to SO₃Thereby corroding downstream pipes. The non-vanadium based catalyst studied at present has generally poor sulfur resistance although the activity is high. SO in flue gas₂It is easy to poison the active sites on the non-vanadium based catalyst, causing the activity of the catalyst to decrease. Therefore, the development of a novel efficient high-sulfur-resistance denitration catalyst is of great significance.

Disclosure of Invention

The invention aims to provide CuSO₄/TiO₂A preparation method of a high-sulfur-resistance denitration catalyst. Reacting CuSO by sol-gel method₄More evenly distributed on the surface of the catalyst, more acid sites are exposed, thereby being beneficial to NH₃Adsorption and activation on the surface of the catalyst. And benefitWith CuSO₄In SO₂The medium and stable property ensures that the catalyst has high sulfur resistance, and overcomes the defect of poor sulfur resistance of the prior non-vanadium-based oxide catalyst. The catalyst prepared by the preparation method can efficiently remove NO in flue gas at 280-380 DEG C_xAnd has high sulfur resistance. The specific invention content is as follows: a method for preparing a CuSO4/TiO2 sulfur-resistant denitration catalyst comprises the following steps:

(1) dissolving butyl titanate in absolute ethyl alcohol to obtain a butyl titanate solution; mixing CuSO₄·5H₂Dissolving O in the mixed solution of water and ethanol to obtain CuSO₄A solution; the concentration of the butyl titanate is 0.2-2 mol/L; CuSO₄The concentration of (A) is 0.02-0.2 mol/L; butyl titanate and CuSO₄The molar ratio of (A) to (B) is 80: 1-8: 1;

(2) adding the butyl titanate solution in the step (1) into CuSO under the stirring condition₄Obtaining sol in the solution; stirring at 200-1000 r/min and at room temperature;

(3) standing and aging the sol obtained in the step (2) for 2-6 h to obtain gel;

(4) drying the gel obtained in the step (3), and roasting to obtain CuSO₄/TiO₂The drying temperature of the catalyst is 100-130 ℃; the roasting temperature is 450-600 ℃, and the heating rate is 2-5 ℃/min.

The volume ratio of water to ethanol in the mixed solution of water and ethanol in the step (1) is 0.2: 1-4: 1.

The invention prepares CuSO by using a sol-gel method₄/TiO₂Denitration catalyst of CuSO₄In TiO₂Uniformly distributed on the carrier, and the TiO is kept₂The catalyst has more acid sites and shows higher denitration activity at 280-380 ℃; and the catalyst utilizes CuSO₄Is not subject to SO₂The property of influence, thus the catalyst possesses high sulfur resistance.

Compared with the prior art, the invention has the beneficial effects that:

(1) the raw materials used in the preparation method are simple, the cost is low, and the influence on the environment is small;

(2) the preparation method of the invention does not need template agent, dispersant and the like, has simple flow and is easy to operate;

(3) CuSO prepared by the invention₄/TiO₂The denitration catalyst has higher specific surface area and more acid sites;

(4) CuSO obtained by the invention₄/TiO₂When ammonia is used as a reducing agent in the denitration catalyst, NO is in the range of 280-380 DEG C_xThe removal rate of the sulfur removal agent is over 90 percent, and the sulfur removal agent has high sulfur resistance.

Drawings

FIG. 1 shows the results of the activity tests of examples 1 to 7 of the present invention;

FIG. 2 is a result of a sulfur resistance test of examples 1 and 3 of the present invention;

FIG. 3 shows NH examples 1 to 7 of the present invention₃-TPD test results and acid number of bits results;

FIG. 4 is a TEM photograph of example 1 of the present invention;

FIG. 5 shows XRD test results of examples 1 to 7 of the present invention;

Detailed Description

The following further illustrates and describes embodiments of the present invention in conjunction with the following example, but the embodiments of the present invention are not limited thereto. If the process parameters are not specifically mentioned, the process can be carried out by conventional techniques.