A low-temperature sulfur dioxide adsorbent, a preparation method and application thereof

Abstract

The application belongs to the technical field of gas adsorbents, and particularly relates to a sulfur dioxide low-temperature adsorbent, a preparation method and application thereof. The sulfur dioxide low-temperature adsorbent comprises a carrier and an active component loaded on the carrier; the carrier is a mixture of aluminum hydroxide and zirconium hydroxide, the mass ratio of the aluminum hydroxide to the zirconium hydroxide is 4:1-4; the active component is metal copper and / or metal potassium; and the mass ratio of the carrier to the active component is 100:4-15. The sulfur dioxide low-temperature adsorbent provided by the application can effectively adsorb sulfur dioxide in flue gas at a working temperature of 280 DEG C, and the sulfur capacity is more than 95 mg / g, so that the advantages of low working temperature, low energy consumption and high sulfur dioxide adsorption efficiency are combined. Moreover, the preparation process is simple and easy to operate, the production process is short, and the production cost is low.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of gas adsorbent, in particular to a sulfur dioxide low-temperature adsorbent, a preparation method and application thereof. BACKGROUND

[0002] Sulfur dioxide is a common atmospheric pollutant. Reducing sulfur dioxide emissions and controlling atmospheric pollution have become one of the important tasks of environmental protection in China. At present, the main sulfur dioxide treatment technologies can be divided into wet treatment technology and dry treatment technology. The wet treatment technology mainly includes limestone-gypsum desulfurization, calcium-sodium double-alkali desulfurization and wet ammonia desulfurization. The dry treatment technology mainly includes activated carbon adsorption method, plasma method and microwave desulfurization method. The currently operating equipment or facilities show that the wet desulfurization has major problems such as high investment cost, large land occupation and equipment corrosion, which affects the normal operation of enterprises and is difficult to meet the national total sulfur emission requirements. The dry treatment technology has attracted great attention from research units and enterprises due to its advantages such as small land occupation, less equipment demand and less investment.

[0003] The working temperature of the commonly used sulfur dioxide adsorbent is mostly greater than 500℃, which needs to set up a heating unit, and the energy consumption is large. CN104190432A discloses a high-efficiency low-temperature denitration and desulfurization activated carbon catalyst, which takes SnCl4 and V2O5 as active components, takes activated carbon as carrier, and takes Fe2O3 and CeO2 as additives. The catalyst has a nitrogen oxide purification efficiency of 85% or more within the range of 70-200℃, but the sulfur capacity is low, only 36mg / g.

[0004] Therefore, the prior art lacks a sulfur dioxide adsorbent with low working temperature and good adsorption capacity, which becomes a technical problem to be solved. SUMMARY

[0005] In view of the above problems, the present application provides a sulfur dioxide low-temperature adsorbent, a preparation method and application thereof. The sulfur dioxide low-temperature adsorbent can realize efficient adsorption of sulfur dioxide at a lower working temperature, greatly reducing the energy consumption and equipment investment cost in the adsorption process.

[0006] In a first aspect of the present application, a sulfur dioxide low-temperature adsorbent is provided, which comprises a carrier and an active component loaded on the carrier; the carrier is a mixture of aluminum hydroxide and zirconium hydroxide, the mass ratio of the aluminum hydroxide to the zirconium hydroxide is 1-4:4; the active component is metal copper and / or metal potassium; the mass ratio of the carrier to the active component is 100:4-15. Further, the active component is metal copper and metal potassium; more further, the molar ratio of the metal copper to the metal potassium is 1:0.5-3.

[0007] In a second aspect, the application provides a preparation method of the aforementioned sulfur dioxide low-temperature adsorbent, comprising the following steps:

[0008] S1, taking aluminum hydroxide coarse powder and zirconium hydroxide coarse powder, drying, grinding and sieving respectively to obtain aluminum hydroxide fine powder and zirconium hydroxide fine powder;

[0009] S2, mixing copper source solution, potassium source solution, aluminum hydroxide fine powder and zirconium hydroxide fine powder for impregnation reaction, and then performing solid-liquid separation, drying and high-temperature calcination to obtain the sulfur dioxide low-temperature adsorbent.

[0010] Further, in step S1, the drying temperature is 70-80℃, the drying time is 3-4h, and the sieving is to 200-300 mesh.

[0011] Further, in step S2, the copper source is copper sulfate, and the mass concentration of the copper source in the copper source solution is 8-15%; the potassium source is potassium chloride, and the mass concentration of the potassium source in the potassium source solution is 10-20%.

[0012] Further, in step S2, the mass-volume ratio of the copper source solution, the potassium source solution, the aluminum hydroxide fine powder and the zirconium hydroxide fine powder is 50mL:50mL:20-30g:30-80g.

[0013] Further, in step S2, the impregnation reaction temperature is 40-70℃, and the impregnation reaction time is 2-3h.

[0014] Further, in step S2, the drying temperature is 60-80℃, and the drying time is 2-3h.

[0015] Further, in step S2, the high-temperature calcination temperature is 300-400℃, and the high-temperature calcination time is 3-4h.

[0016] In a third aspect, the application provides the use of the aforementioned sulfur dioxide low-temperature adsorbent in reducing the sulfur dioxide emission concentration in flue gas.

[0017] The application has the following advantages:

[0018] 1. The sulfur dioxide low-temperature adsorbent provided by the application can uniformly distribute active metals on the carrier, and the complex formed by the active metals and the carrier can reduce the activation energy of the reaction between sulfur dioxide and the active sites of the adsorbent, so that the sulfur dioxide in the flue gas can be effectively adsorbed at a working temperature of 280℃, and the sulfur capacity is more than 95mg / g, thus having the advantages of low working temperature, low energy consumption and high sulfur dioxide adsorption efficiency.

[0019] 2. The preparation process of the sulfur dioxide low-temperature adsorbent provided by the application is simple and easy to operate, the production process is short, and the production cost is low. DETAILED DESCRIPTION

[0020] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only some, but not all of the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of the present application.

[0021] Embodiment 1

[0022] The embodiment provides a sulfur dioxide low-temperature adsorbent, which is prepared by the following method: 100 g of aluminum hydroxide coarse powder and 100 g of zirconium hydroxide coarse powder are dried at 80 DEG C for 3 h respectively, and are ground into fine powder by a mortar, and are sieved to be used. 200 mL of 8% copper sulfate aqueous solution is prepared, 30 g of 200-mesh zirconium hydroxide fine powder and 30 g of 200-mesh aluminum hydroxide fine powder are added into 100 mL of 8% copper sulfate aqueous solution, and are stirred at 40 DEG C for 3 h to obtain a uniform mixture, then the mixture is filtered to obtain a slurry, the slurry is dried in a drying box at 60 DEG C for 3 h, and then is calcined at 300 DEG C for 3 h, and the sulfur dioxide low-temperature adsorbent is obtained.

[0023] Embodiment 2

[0024] The embodiment provides a sulfur dioxide low-temperature adsorbent, which is prepared by the following method: 100 g of aluminum hydroxide coarse powder and 100 g of zirconium hydroxide coarse powder are dried at 70 DEG C for 4 h respectively, and are ground into fine powder by a mortar, and are sieved to be used. 200 mL of 15% copper sulfate aqueous solution is prepared, 40 g of 300-mesh zirconium hydroxide fine powder and 30 g of 300-mesh aluminum hydroxide fine powder are added into 100 mL of 15% copper sulfate aqueous solution, and are stirred at 70 DEG C for 2 h to obtain a uniform mixture, then the mixture is filtered to obtain a slurry, the slurry is dried in a drying box at 70 DEG C for 3 h, and then is calcined at 400 DEG C for 3 h, and the sulfur dioxide low-temperature adsorbent is obtained.

[0025] Embodiment 3

[0026] The embodiment provides a low-temperature sulfur dioxide adsorbent, which is prepared by the following method: 100g of aluminum hydroxide coarse powder and 100g of zirconium hydroxide coarse powder are dried at 80 DEG C for 3h respectively, are ground into fine powder by a mortar, are sieved, and are reserved. 200ml of 15% copper sulfate aqueous solution and 200ml of 10% potassium chloride aqueous solution are prepared, 50ml of the two solutions are taken respectively and are uniformly mixed to obtain a mixed solution. 30g of 300-mesh zirconium hydroxide fine powder and 30g of 200-mesh aluminum hydroxide fine powder are added into 100ml of the mixed solution, are stirred at 50 DEG C for 3h to obtain a uniform mixture, are filtered to obtain slurry, and the slurry is dried in a drying box at 80 DEG C for 2h, and then is calcined at 400 DEG C for 3h.

[0027] Example 4

[0028] The embodiment provides a low-temperature sulfur dioxide adsorbent, which is prepared by the following method: 100g of aluminum hydroxide coarse powder and 100g of zirconium hydroxide coarse powder are dried at 80 DEG C for 3h respectively, are ground into fine powder by a mortar, are sieved, and are reserved. 200ml of 15% copper sulfate aqueous solution and 200ml of 10% potassium chloride aqueous solution are prepared, 50ml of the two solutions are taken respectively and are uniformly mixed to obtain a mixed solution. 30g of 300-mesh zirconium hydroxide fine powder and 30g of 200-mesh aluminum hydroxide fine powder are added into 100ml of the mixed solution, are stirred at 50 DEG C for 3h to obtain a uniform mixture, are filtered to obtain slurry, and the slurry is dried in a drying box at 80 DEG C for 2h, and then is calcined at 400 DEG C for 3h.

[0029] Comparative Example 1

[0030] The comparative example provides a low-temperature sulfur dioxide adsorbent, which is prepared by the following method: 100g of iron hydroxide coarse powder is dried at 80 DEG C for 3h, is ground into fine powder by a mortar, is sieved, and is reserved. 200ml of 8% copper sulfate aqueous solution is prepared, 60g of 200-mesh iron hydroxide fine powder is added into 100ml of the 8% copper sulfate aqueous solution, is stirred at 40 DEG C for 3h to obtain a uniform mixture, is filtered to obtain slurry, and the slurry is dried in a drying box at 60 DEG C for 3h, and then is calcined at 300 DEG C for 3h.

[0031] Comparative Example 2

[0032] The comparative example provides a sulfur dioxide low-temperature adsorbent, which is prepared by the following method: 100 g of aluminum hydroxide coarse powder and 100 g of zirconium hydroxide coarse powder are dried at 80°C for 3 h, ground into fine powder with a mortar, and sieved for standby use. An 8% magnesium chloride aqueous solution of 200 mL is prepared, 30 g of 200-mesh zirconium hydroxide fine powder and 30 g of 200-mesh aluminum hydroxide fine powder are added to 100 mL of the 8% magnesium chloride aqueous solution, and stirred at 40°C for 3 h to obtain a uniform mixture, and then the slurry is obtained by suction filtration, dried in a drying oven at 60°C for 3 h, and then calcined at 300°C for 3 h.

[0033] Test example

[0034] The sulfur dioxide low-temperature adsorbents prepared in Examples 1-4 and Comparative Examples 1-2 are subjected to adsorption and regeneration evaluation experiments, wherein the adsorption temperature is controlled at 280°C. The sulfur dioxide low-temperature adsorbent is loaded in a fixed bed reactor, and when the sulfur dioxide concentration at the outlet of the fixed bed reactor is greater than 100 mg / m 3 , it is considered that the adsorption process is complete. In the measurement of the sulfur capacity of the adsorbent, the concentration of sulfur-containing gas in the outlet gas of the fixed bed reactor (loaded with the adsorbent) is detected by a gas chromatograph equipped with a TCD detector, and the corresponding SO2 content is analyzed according to SY / T6537-2002 (Natural Gas Purification Plant Gas and Solution Analysis Method). In the determination of the adsorption sulfur capacity of SO2, the gas composition except water is 1.5% SO2 concentration, 3% O2 concentration, 25% CO2 concentration, and the balance is N2. The calculation method of the adsorption sulfur capacity of SO2 is as follows:

[0035]

[0036] wherein C is the concentration of SO2 (unit: mol / L), V is the volume of gas passing through the adsorbent (unit: L), 64 is the molar mass of SO2, 22.4 is the molar volume of SO2, and M is the mass of the adsorbent (unit: g).

[0037]

[0038] From the above table, the sulfur capacity of the sulfur dioxide low-temperature adsorbents of the embodiments 1-4 of the present application is above 95 mg / g, which is comparable to that of the conventional sulfur dioxide adsorbents and stable in performance. The sulfur capacity of the adsorbents of the comparative examples 1-2 is significantly lower than that of the adsorbents of the embodiments 1-4, which indicates that the carrier and active component defined in the present application can further improve the sulfur dioxide adsorption effect and is beneficial to the preparation of the sulfur dioxide adsorbent with better adsorption performance. In addition, compared with the adsorption temperature of the conventional sulfur dioxide adsorbents which is generally above 500℃, the adsorption temperature (280℃) of the sulfur dioxide adsorbents prepared in the embodiments of the present application is significantly lower, which is beneficial to reduce the energy consumption and production cost.

[0039] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above-described embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, and these simple modifications all belong to the protection scope of the present application.

Claims

1. A low temperature sulfur dioxide adsorbent characterized by, It comprises a carrier and an active component supported on the carrier; the carrier is a mixture of aluminum hydroxide and zirconium hydroxide, the mass ratio of the aluminum hydroxide to the zirconium hydroxide is 1-4:4; the active component is metallic copper, or metallic copper and metallic potassium; the mass ratio of the carrier to the active component is 100:4-15; The preparation method of the sulfur dioxide low-temperature adsorbent comprises the following steps: S1. Take aluminum hydroxide coarse powder and zirconium hydroxide coarse powder, dry, grind and sieve them respectively to obtain aluminum hydroxide fine powder and zirconium hydroxide fine powder; S2. Mix copper source solution, or copper source solution and potassium source solution, with the aluminum hydroxide fine powder and the zirconium hydroxide fine powder to perform impregnation reaction, and then perform solid-liquid separation, drying and high-temperature calcination to obtain the sulfur dioxide low-temperature adsorbent; the copper source in the copper source solution is copper sulfate, the potassium source in the potassium source solution is potassium chloride, the temperature of the high-temperature calcination is 300-400 ℃, and the time of the high-temperature calcination is 3-4 h.

2. The sulfur dioxide cryosorbent of claim 1, wherein, The active component is metallic copper and metallic potassium; the molar ratio of the metallic copper to the metallic potassium is 1:0.5-3.

3. The method of claim 2, wherein the sulfur dioxide cryosorbent is prepared by, The preparation method of the sulfur dioxide low-temperature adsorbent comprises the following steps: S1. Take aluminum hydroxide coarse powder and zirconium hydroxide coarse powder, dry, grind and sieve them respectively to obtain aluminum hydroxide fine powder and zirconium hydroxide fine powder; S2. Mix copper source solution, potassium source solution, aluminum hydroxide fine powder and zirconium hydroxide fine powder to perform impregnation reaction, and then perform solid-liquid separation, drying and high-temperature calcination to obtain the sulfur dioxide low-temperature adsorbent; the copper source in the copper source solution is copper sulfate, the potassium source in the potassium source solution is potassium chloride, the temperature of the high-temperature calcination is 300-400 ℃, and the time of the high-temperature calcination is 3-4 h.

4. The method of claim 3, wherein the sulfur dioxide adsorbent is prepared by the steps of: In step S1, the temperature of the drying is 70-80 ℃, the time of the drying is 3-4 h, and the sieving is to 200-300 mesh.

5. The method of claim 3, wherein the sulfur dioxide adsorbent is prepared by the steps of: In step S2, the mass concentration of the copper source in the copper source solution is 8-15%, and the mass concentration of the potassium source in the potassium source solution is 10-20%.

6. The method of claim 3, wherein the sulfur dioxide adsorbent is prepared by the steps of: In step S2, the mass-volume ratio of the copper source solution, the potassium source solution, the aluminum hydroxide fine powder and the zirconium hydroxide fine powder is 50 mL:50 mL:20-30 g:30-80 g.

7. The method of claim 3, wherein the sulfur dioxide adsorbent is prepared by the steps of: In step S2, the temperature of the impregnation reaction is 40-70 ℃, and the time of the impregnation reaction is 2-3 h.

8. The method of claim 3, wherein the sulfur dioxide adsorbent is prepared by the steps of: In step S2, the temperature of the drying is 60-80 ℃, and the time of the drying is 2-3 h.

9. The sulfur dioxide low-temperature adsorbent according to claim 1 or 2 is applied to reducing the concentration of sulfur dioxide emission in flue gas.

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