CN109603472B - Adsorbent and method for treating waste gas containing sulfur dioxide - Google Patents
Adsorbent and method for treating waste gas containing sulfur dioxide Download PDFInfo
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- CN109603472B CN109603472B CN201811444069.8A CN201811444069A CN109603472B CN 109603472 B CN109603472 B CN 109603472B CN 201811444069 A CN201811444069 A CN 201811444069A CN 109603472 B CN109603472 B CN 109603472B
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
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Abstract
The invention provides an adsorbent for treating waste gas containing sulfur dioxide and a method thereof, wherein the adsorbent comprises the following components in percentage by weight: 10-20% of diphenyl sulfoxide, 5-10% of 2, 3-diphenyl piperazine, 15-30% of tetraethylene glycol dimethyl ether, 0.5-2% of soluble copper salt and 40-60% of deionized water. The adsorbent for treating the waste gas containing the sulfur dioxide, provided by the invention, has high absorption rate and large absorption capacity for the sulfur dioxide gas, also has very high desorption rate, is high in adsorption selectivity, has no adsorption effect on other components in the waste gas, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of gas separation, in particular to an adsorbent and a method for treating waste gas containing sulfur dioxide.
Background
SO2Is the main material for forming acid rain, and is mainly from flue gas emission of coal-fired power plants. SO abundantly present in air2Not only harmful to human health, but also formed when exposed to waterAcid rain causes great harm to forests, soils, lakes and other systems, SO that SO must be strengthened2And (4) controlling the emission. The adsorption method has the advantages of low investment, low energy consumption, simple equipment, no secondary pollution and the like, and becomes a flue gas desulfurization method with the greatest development prospect. At present, the mainstream flue gas desulfurization technology utilizes various alkaline absorbents or adsorbents to capture SO in flue gas2And converting it into more stable sulfur-containing compounds. Common methods for desulfurizing flue gas include limestone-gypsum method, ammonia acid method, magnesium oxide method, active coke method, and the like. Among them, the limestone-gypsum desulfurization technique, which is the most widely used technique in the flue gas desulfurization method, increases the desulfurization efficiency, but the amount of waste liquid and waste residue generated in the desulfurization process is large, and these by-products need to be specially treated or utilized. The main methods adopted for wet desulphurization currently include a sodium-alkali method: SO absorption by using alkali liquor washing flue gas2The method can not cause the problems of scaling and blockage in the absorption tower and can treat the flue gas on a large scale. However, the absorption method is a gas-liquid two-phase reaction, a part of SO2The liquid escapes without fully reacting with the alkali liquor, thus the utilization rate of the alkali liquor is low, and the selective absorption of the alkali liquor is poor, such as CO2Such acid gases can be absorbed, resulting in absorption of SO2The effective capacity of (2) is reduced and thus the desulfurization rate is low.
Disclosure of Invention
Aiming at the problems of low alkali liquor utilization rate and low desulfurization rate in the existing absorption of sulfur dioxide-containing waste gas, the invention provides an absorbent and a method for treating sulfur dioxide-containing waste gas.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an adsorbent for treating waste gas containing sulfur dioxide comprises the following components in percentage by weight: 10-20% of diphenyl sulfoxide, 5-10% of 2, 3-diphenyl piperazine, 15-30% of tetraethylene glycol dimethyl ether, 0.5-2% of soluble copper salt and 40-60% of deionized water.
Compared with the prior art, the adsorbent for treating the waste gas containing the sulfur dioxide is a two-phase adsorbent, and a liquid-liquid two phase after adsorption is easy to separate; by adding soluble copper salt, the adsorbent is remarkably improvedThe adsorption performance and the selective absorption performance of the adsorbent ensure that the prepared adsorbent has no adsorption effect on other components in the waste gas, greatly improves the absorption capacity of the adsorbent on sulfur dioxide, and has the concentration of 50000mg/m for the sulfur dioxide3The flue gas can be effectively absorbed and treated, and the desulfurization rate reaches more than 99 percent. The adsorbent for treating the waste gas containing the sulfur dioxide, provided by the invention, has the advantages of high absorption speed, strong absorption capacity and strong selectivity compared with the existing sulfur dioxide adsorbent through the synergistic effect of the components.
Preferably, the soluble copper salt is at least one of copper sulfate, copper nitrate or copper chloride.
The preferred soluble copper salts may work better in concert with other components to increase the adsorption capacity and selectivity of the adsorbent.
The invention also provides a preparation method of the adsorbent for treating the waste gas containing the sulfur dioxide, which at least comprises the following steps: weighing the components according to the designed proportion, uniformly mixing the components, heating to 40-50 ℃, and stirring for 0.5-1.5h to obtain the adsorbent.
The preparation method is simple and feasible, and the components can interact with each other by the preparation method to synergistically enhance the adsorption performance of the adsorbent. The prepared absorbent has high absorption capacity for sulfur dioxide gas and high selective absorption capacity, eliminates most of effective desulfurization space occupied by interference gas, greatly improves the effective space capable of absorbing sulfur dioxide, and simultaneously avoids the problem of low desorption rate of the absorbent caused by the fact that the interference gas occupies the absorbent.
The invention also provides a method for treating the waste gas containing sulfur dioxide, which adopts the adsorbent to absorb the sulfur dioxide in the waste gas.
Preferably, the method for treating the sulfur dioxide-containing waste gas comprises the following steps:
introducing the waste gas containing sulfur dioxide into the adsorbent, detecting the content of outlet sulfur dioxide, stopping introducing when the concentration of sulfur dioxide reaches 0.8mg/L, adding an alkaline solution under the condition of stirring, separating out a water phase, and continuously recycling the obtained organic phase for preparing a new adsorbent.
The waste gas containing sulfur dioxide is introduced into the adsorbent, then alkaline solution is added, sulfur dioxide reacts with the alkaline solution to generate sulfite or bisulfite solution, the sulfite or bisulfite solution is layered with the organic phase, and the regeneration of the organic phase in the adsorbent can be realized by simple liquid separation operation subsequently, thereby simplifying the operation and reducing the energy consumption.
The adsorbent provided by the invention has the advantages of high absorption speed and strong selectivity, can improve the treatment efficiency of waste gas, reduce the usage amount of liquid caustic soda, obviously reduce the cost for treating the waste gas and has wide application prospect in industrial application when being applied to the treatment of industrial waste gas containing sulfur dioxide.
Preferably, the alkaline solution is a sodium hydroxide solution or a sodium carbonate solution.
Sodium hydroxide and sodium carbonate can make SO in adsorbent2Quickly resolving out the Na and generating the Na2SO3And NaHSO3Can release high-concentration pure SO again by heating2Gas, which is applied to other chemical fields.
Optionally, the Na produced may also be2SO3And NaHSO3The solution reacts with quicklime or slaked lime, the lower layer is precipitated calcium sulfite, the upper clear liquid is sodium hydroxide solution, and the obtained sodium hydroxide solution can be used for desorbing SO in the adsorbent2The gas further saves the consumption of liquid caustic soda and further reduces the cost of waste gas treatment.
Preferably, the speed of the sulfur dioxide-containing waste gas introduced into the adsorbent is 5-15m3/h。
More preferably, the speed of the sulfur dioxide-containing waste gas introduced into the adsorbent is 10m3/h。
The preferred exhaust gas discharge speed can enable the adsorbent to more completely adsorb sulfur dioxide gas, and can also improve the treatment efficiency.
Preferably, the concentration of the alkaline solution is 15 to 30 wt%.
The concentration of the preferred alkaline solution can completely decompose sulfur dioxide gas in the adsorbent, and the dosage of the alkaline solution can be saved.
If the alkali liquor is sodium hydroxide solution, desorbing SO2In the case of gas, 300-550g of 15-30wt% sodium hydroxide solution per liter of adsorbent is added.
If the alkali liquor is sodium carbonate solution, desorbing SO2In the case of gas, 360-750g of 15-30wt% sodium carbonate solution per liter of adsorbent is added.
Preferably, the stirring speed is 100-.
The alkaline solution is added at a lower stirring speed, so that the alkaline solution can fully react with sulfur dioxide in the adsorbent.
Preferably, the adsorption temperature is 20-60 ℃.
The adsorbent provided by the invention has higher adsorption capacity for sulfur dioxide gas within the range of 20-60 ℃.
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.
Example 1
An adsorbent for treating sulfur dioxide-containing waste gas: 19.5 percent of diphenyl sulfoxide, 10 percent of 2, 3-diphenyl piperazine, 30 percent of tetraethylene glycol dimethyl ether, 0.5 percent of copper sulfate and 40 percent of deionized water.
The preparation method of the adsorbent comprises the following steps:
weighing the components according to the designed proportion, uniformly mixing the components, heating to 40 ℃, and stirring at the speed of 300rpm for 1h to obtain the adsorbent.
The method for treating the waste gas containing the sulfur dioxide by using the adsorbent comprises the following steps:
under the condition of 30 ℃, the waste gas containing sulfur dioxide is heated to 5m3Introducing into the adsorbent at a speed of/h, detecting the content of outlet sulfur dioxide, and when the concentration of sulfur dioxide reaches 0.8mgThe aeration was stopped, 750g of a 15 wt.% sodium carbonate solution per liter of adsorbent were added at a stirring speed of 100rpm, the aqueous phase was separated off and the organic phase obtained was recycled.
Example 2
An adsorbent for treating sulfur dioxide-containing waste gas: 15% of diphenyl sulfoxide, 7% of 2, 3-diphenyl piperazine, 27% of tetraethylene glycol dimethyl ether, 1% of copper nitrate and 50% of deionized water.
The preparation method of the adsorbent comprises the following steps:
weighing the components according to the designed proportion, uniformly mixing the components, heating to 45 ℃, and stirring at the speed of 500rpm for 0.5h to obtain the adsorbent.
The method for treating the waste gas containing the sulfur dioxide by using the adsorbent comprises the following steps:
the sulfur dioxide-containing waste gas is heated to 8m under the condition of 20 DEG C3Introducing the mixture into the adsorbent at a discharge speed of/h, detecting the content of sulfur dioxide at an outlet, stopping introducing the mixture when the concentration of the sulfur dioxide reaches 0.8mg/L, adding 550g of 20 wt% sodium carbonate solution into each liter of the adsorbent at a stirring speed of 150rpm, separating out a water phase, and continuously recycling the obtained organic phase.
Example 3
An adsorbent for treating sulfur dioxide-containing waste gas: 20% of diphenyl sulfoxide, 5% of 2, 3-diphenyl piperazine, 15% of tetraethylene glycol dimethyl ether, 2% of copper chloride and 58% of deionized water.
The preparation method of the adsorbent comprises the following steps:
weighing the components according to the designed proportion, uniformly mixing the components, heating to 50 ℃, and stirring at the speed of 450rpm for 1.5h to obtain the adsorbent.
The method for treating the waste gas containing the sulfur dioxide by using the adsorbent comprises the following steps:
the sulfur dioxide-containing waste gas is heated to 10m under the condition of 60 DEG C3Introducing into the adsorbent at a discharge speed of/h, detecting outlet sulfur dioxide content, stopping introducing when sulfur dioxide concentration reaches 0.8mg/L, and stirring at 100rpm450g of 25 wt% sodium carbonate solution is added into each liter of adsorbent, a water phase is separated, and the obtained organic phase can be continuously recycled.
Example 4
An adsorbent for treating sulfur dioxide-containing waste gas: 10% of diphenyl sulfoxide, 6% of 2, 3-diphenyl piperazine, 23% of tetraethylene glycol dimethyl ether, 1% of copper sulfate and 60% of deionized water.
The preparation method of the adsorbent comprises the following steps:
weighing the components according to the designed proportion, uniformly mixing the components, heating to 48 ℃, and stirring at the speed of 400rpm for 1.5h to obtain the adsorbent.
The method for treating the waste gas containing the sulfur dioxide by using the adsorbent comprises the following steps:
under the condition of 40 ℃, the waste gas containing sulfur dioxide is heated to 15m3And introducing the mixture into the adsorbent at a discharge speed of/h, detecting the content of outlet sulfur dioxide, stopping introducing the mixture when the concentration of the sulfur dioxide reaches 0.8mg/L, adding 360g of 30wt% sodium carbonate solution into each liter of the adsorbent at a stirring speed of 200rpm, separating out a water phase, and continuously recycling the obtained organic phase.
Comparative example 1
An adsorbent for treating sulfur dioxide-containing waste gas: 10% of diphenyl sulfoxide, 6% of 2, 3-diphenyl piperazine, 23% of tetraethylene glycol dimethyl ether and 61% of deionized water.
The preparation method of the adsorbent comprises the following steps:
weighing the components according to the designed proportion, uniformly mixing the components, heating to 48 ℃, and stirring at the speed of 400rpm for 1.5h to obtain the adsorbent.
The method for treating the sulfur dioxide-containing waste gas by using the adsorbent is the same as that of example 4, and the details are omitted here.
Comparative example 2
An adsorbent for treating sulfur dioxide-containing waste gas: 10% of dimethyl sulfoxide, 6% of 2, 3-diphenyl piperazine, 23% of tetraethylene glycol dimethyl ether, 1% of copper sulfate and 60% of deionized water.
Weighing the components according to the designed proportion, uniformly mixing the components, heating to 48 ℃, and stirring at the speed of 400rpm for 1.5h to obtain the adsorbent.
The method for treating the sulfur dioxide-containing waste gas by using the adsorbent is the same as that of example 4, and the details are omitted here.
Comparative example 3
An adsorbent for treating sulfur dioxide-containing waste gas: 10% of diphenyl sulfoxide, 6% of piperazine, 23% of tetraethylene glycol dimethyl ether, 1% of copper sulfate and 60% of deionized water.
Weighing the components according to the designed proportion, uniformly mixing the components, heating to 48 ℃, and stirring at the speed of 400rpm for 1.5h to obtain the adsorbent.
The method for treating the sulfur dioxide-containing waste gas by using the adsorbent is the same as that of example 4, and the details are omitted here.
In order to examine the desulfurization performance of the adsorbents prepared in examples 1 to 4 and comparative examples 1 to 3, SO was used2、CO2And N2The desulfurization performance of the simulated flue gas is inspected by absorption experiments of various adsorbents, the volume of the adsorbent is 200mL, and SO is added2Is about 0.5% by volume, CO2Is 20%, and the speed of the simulated smoke gas passing into the adsorbent is 10m3The adsorption temperature is 25 ℃, and the SO in the simulated flue gas and the absorbed tail gas2With SO at a mass concentration of2Measuring with a flue gas analyzer to obtain SO in the absorption liquid2The concentrations of (A) were analyzed by iodometry, and the results are shown in Table 1
TABLE 1
Note: the saturated absorption time refers to the absorption time required when the outlet concentration of the simulated flue gas after desulfurization and absorption reaches the national emission standard (0.8 mg/L).
Compared with the common method of only adopting sodium carbonate solution or sodium hydroxide solution to absorb sulfur dioxide in the waste gas, the adsorbent provided by the invention can save 30% of the using amount of sodium carbonate or sodium hydroxide, remarkably reduce the using amount of sodium carbonate or sodium hydroxide and reduce the cost for treating the waste gas.
In conclusion, the adsorbent for treating the waste gas containing the sulfur dioxide provided by the invention has high absorption rate and large absorption capacity for the sulfur dioxide gas, also has very high desorption rate, is high in adsorption selectivity, has no adsorption effect on other components in the waste gas, and has wide application prospect.
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 or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. An adsorbent for treating waste gas containing sulfur dioxide is characterized by comprising the following components in percentage by weight: 10-20% of diphenyl sulfoxide, 5-10% of 2, 3-diphenyl piperazine, 15-30% of tetraethylene glycol dimethyl ether, 0.5-2% of soluble copper salt and 40-60% of deionized water; wherein the soluble copper salt is at least one of copper sulfate, copper nitrate or copper chloride.
2. A method for preparing an adsorbent for treating a sulfur dioxide-containing waste gas according to claim 1, comprising at least the steps of: weighing the components according to the designed proportion, uniformly mixing the components, heating to 40-50 ℃, and stirring for 0.5-1.5h to obtain the adsorbent.
3. A method for treating a sulfur dioxide-containing waste gas, characterized in that the sulfur dioxide in the waste gas is absorbed by using the adsorbent according to claim 1.
4. A method according to claim 3 for treating a sulphur dioxide containing off-gas, comprising the steps of:
introducing the waste gas containing sulfur dioxide into the adsorbent of claim 1, detecting the content of outlet sulfur dioxide, stopping introducing when the concentration of sulfur dioxide reaches 0.8mg/L, adding an alkaline solution under the condition of stirring, separating out a water phase, and continuously recycling the obtained organic phase.
5. The method of treating a sulfur dioxide-containing waste gas as claimed in claim 4, wherein said alkaline solution is a sodium hydroxide solution or a sodium carbonate solution.
6. The process for the treatment of a sulfur dioxide-containing waste gas as claimed in claim 4, wherein the sulfur dioxide-containing waste gas is passed into the adsorbent at a velocity of 5 to 15m3/h。
7. The method of treating a sulfur dioxide-containing waste gas as claimed in claim 4, wherein the concentration of said alkaline solution is 15 to 30 wt%.
8. The method for treating a sulfur dioxide-containing waste gas as claimed in claim 4, wherein the stirring speed is 100-300 rpm.
9. The process for the treatment of a sulfur dioxide-containing waste gas as claimed in claim 4, wherein the adsorption temperature is 20 to 60 ℃.
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Address after: 061000 East side of National Highway 105, Dazhang Village, Dongguang County, Cangzhou City, Hebei Province Patentee after: Caike Huayu Chemical Co.,Ltd. Patentee after: Caike Technology Research and Development (Beijing) Co.,Ltd. Address before: 061000 East of Dazhang Section of 104 National Highway, Dongguang County, Cangzhou City, Hebei Province Patentee before: HEBEI CAIKE CHEMICAL Co.,Ltd. Patentee before: CAIKE TECHNOLOGY (BEIJING) CO.,LTD. |