CN111185079A - Resourceful treatment method for acid gas in incineration flue gas - Google Patents
Resourceful treatment method for acid gas in incineration flue gas Download PDFInfo
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- B01D53/14—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 by absorption
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- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/64—Thiosulfates; Dithionites; Polythionates
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/14—Preparation of sulfites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2258/0283—Flue gases
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Abstract
The invention discloses a resource treatment method of acid gas in incineration flue gas, which designs a multistage absorption device by utilizing the mutual influence of the solubility of different acids in water, the acid gas can be used for preparing sulfuric acid, hydrochloric acid and sodium sulfite with higher purity after absorption treatment, the sodium sulfite can also react with sulfur to prepare sodium thiosulfate pentahydrate, and the obtained product can be used as a chemical raw material or sold as a commodity. The method mainly uses water as an absorption medium, has the characteristics of simple equipment, good absorption effect, low cost, effective recycling of waste and the like, and is a green and environment-friendly treatment method. The flue gas treatment method is suitable for the purification treatment of the flue gas of waste incineration, chemical waste incineration, metallurgical solid waste incineration, coal-fired boilers, oil-fired boilers, thermal power plants, coking plants and other acidic gases containing sulfur, chlorine and the like.
Description
Technical Field
The invention relates to the technical field of flue gas treatment, in particular to an absorption and recycling process of acid gas in incineration flue gas.
Background
With the continuous development of economy, people have higher and higher requirements on the environment, and the efficient treatment and recycling of various wastes become the premise of the healthy survival of citizens and the sustainable development of society. The incineration method is a waste treatment method, which means that under the condition of high temperature, combustible substances in the waste and oxygen in the air undergo violent chemical reaction, heat is released and the combustible substances are converted into high-temperature gas and a small amount of solid residues with stable properties. Because the incineration method has large treatment capacity, good volume reduction and thorough harmlessness, the incineration method is more and more widely used for the treatment of household garbage, the treatment of industrial three wastes and the like. However, because many incinerated substances contain more sulfur and chlorine elements, a large amount of acid gases which may generate secondary pollutants remain in the flue gas tail gas after the flue gas generated by incineration is treated by various deacidification processes, such as: SO (SO)2、SO3And HCl and the like, and the HCl and the like are required to enter an absorption tower for absorption and purification before being discharged so as to control the content of the acid gas in the discharged flue gas and ensure that the flue gas reaches the standard for discharge. In other various industries involving combustion flue gas emissions, acid gases in the flue gas also need to be absorbed to purify the flue gas and achieve the emission standards.
The invention patent CN101829468 discloses a flue gas purification method for waste incineration, the flue gas tail gas enters an absorption tower after the incineration flue gas is cooled and subjected to cloth bag dust removal, and the absorption tower uses sodium hydroxide solution as an acid absorbent to remove acid gas so as to make the flue gas emission reach the standard. The invention patent CN109297023 discloses a waste incineration system, wherein after flue gas passes through a semi-dry type quenching absorption tower and a dry reactor, tail gas is absorbed by alkali liquor to remove residual acid gas and then is discharged. The invention patent CN110006050 discloses a hazardous waste incineration flue gas purification system, which finally adopts sodium hydroxide solution to absorb residual acid gas after being treated by a plurality of deacidification processes. In many similar reports, the alkali liquor absorption mode is mostly adopted for residual acid gas in the flue gas and tail gas before the discharge, the treatment cost is high, and simultaneously, a large amount of high-salinity wastewater is difficult to treat.
The invention patent CN107998788 discloses a method for treating waste gas of an incinerator, acid gas is absorbed by spraying water before the emission of flue gas, the cost is saved by using water as an absorbent, but the obtained acid liquid cannot be recycled; utility model CN208846437 discloses a high chlorine danger is useless burns purifier of flue gas, washes flue gas tail gas before the alkali wash absorption to be used for the flying dust washing with the acid wastewater that produces after the washing, reduced the pickling cost, but produced acidizing fluid only can be in the inside use of system. In such reports, although the cost is reduced by using water for absorption compared with alkali liquor for absorption, the waste acid generated by absorption cannot be purified into single-component acid for recycling.
Disclosure of Invention
Based on the problems, the invention aims to provide a resource treatment method for acid gas in incineration flue gas, a multistage absorption device is designed by utilizing the mutual influence of the solubility of different acids in water, the acid gas can be absorbed and treated to prepare sulfuric acid, hydrochloric acid and sodium sulfite with higher purity, the sodium sulfite can also react with sulfur to prepare sodium thiosulfate pentahydrate, and the obtained product can be used as a chemical raw material or sold as a commodity. The method mainly uses water as an absorption medium, has the characteristics of simple equipment, good absorption effect, low cost, effective recycling of waste and the like, and is a green and environment-friendly treatment method. The method is suitable for the purification treatment of the flue gas of waste incineration, chemical waste incineration, metallurgical solid waste incineration, coal-fired boilers, oil-fired boilers, thermal power plants, coking plants and other acidic gases containing sulfur, chlorine and the like.
The resource treatment method of the acid gas in the incineration flue gas comprises the following steps:
(1) the incineration flue gas is sequentially subjected to cooling and filtering dust removal pretreatment;
(2) by SO3The absorption tower is used for absorbing SO in the pretreated flue gas3Performing an adsorption treatment, the SO3A heat exchanger is arranged in the absorption tower to ensure that the absorption temperature is 75-90 ℃;
(3) via SO3Continuously feeding the flue gas treated by the absorption tower into a multistage HCl absorption tower to absorb HCl gas in the flue gas;
(4) the flue gas treated by the HCl absorption tower enters SO2An absorption tower for absorbing SO in the flue gas2A gas;
(5) via SO2The flue gas absorbed by the absorption tower is introduced into a chimney and is discharged into the atmosphere.
Preferably, the incineration flue gas in the step (1) includes one of flue gas generated in the incineration process of waste, coal and fuel oil, or incineration flue gas generated in a thermal power plant and a coke-oven plant and other acidic incineration flue gas containing sulfur and chlorine.
Preferably, the pretreatment in the step (1) is to pretreat the flue gas by a quenching tower and a bag-type dust remover.
Preferably, the SO3The absorption tower takes water as an absorption medium, the sulfuric acid in the absorption tower is removed and new water is supplemented when the concentration reaches a certain concentration, and the concentration of the sulfuric acid in the removal of the sulfuric acid is 50-90%. In the initial absorption stage of the step, sulfuric acid, sulfurous acid and hydrochloric acid coexist in the absorption liquid, the sulfurous acid and the hydrochloric acid are gradually reduced along with the increase of the concentration of the sulfuric acid in the absorption liquid and are converted into gas again to enter the flue gas, new water is removed and supplemented when the concentration of the sulfuric acid in the absorption tower reaches 50-90%, and the removed sulfuric acid can be used or sold as a commodity.
Further preferably, the concentration of the sulfuric acid at the time of removal is 65% to 75%.
Preferably, water is adopted by the HCl absorption towers as an absorption medium, the absorption stages of the multistage HCl absorption towers are 1-10 stages, hydrochloric acid and sulfurous acid coexist in the absorption liquid at the initial stage of the step, and the sulfurous acid is gradually reduced along with the increase of the concentration of the hydrochloric acid and is converted into a gas form again to enter the flue gas.
Further preferably, the absorption stages of the multistage HCl absorption tower are 2-5 stages.
Preferably, the flue gas passes through a plurality of stages of HCl absorption towers, when the concentration of hydrochloric acid in the first-stage HCl absorption tower is 15% -35%, the flue gas is removed, the removed hydrochloric acid can be used or sold as a commodity, the flue gas is absorbed by the next-stage HCl absorption tower and transferred to the previous-stage HCl absorption tower, and the last-stage HCl absorption tower replenishes new water.
Preferably, the SO2The absorption liquid in the absorption tower is alkali liquor, and the alkali liquor is one of sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution.
Further preferably, the SO2Absorbing liquid in the absorption tower is saturated and then is moved out, the moved absorbing liquid is treated to obtain sodium sulfite and mother liquor, the sodium sulfite can react with sulfur to obtain sodium thiosulfate pentahydrate, the sodium sulfite and the sodium thiosulfate pentahydrate can be used or sold as commodities, and the mother liquor is filtered and then returns to SO2The absorption tower is used as an absorption liquid.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention designs a multistage absorption device by utilizing the mutual influence of the solubility of different acids in the flue gas in water, the acid gas can be used for preparing sulfuric acid, hydrochloric acid and sodium sulfite with higher purity after absorption treatment, the sodium sulfite can also react with sulfur to prepare sodium thiosulfate pentahydrate, and the obtained product can be used as a chemical raw material or sold as a commodity;
2) the invention mainly uses water as an absorption medium, has the characteristics of simple equipment, good absorption effect, low cost, effective recycling of waste and the like, and is a green and environment-friendly treatment method;
3) the flue gas purification method is suitable for the purification treatment of the flue gas of waste incineration, chemical waste incineration, metallurgical solid waste incineration, coal-fired boilers, oil-fired boilers, thermal power plants, coking plants and other acidic gases containing sulfur, chlorine and the like.
Drawings
Fig. 1 is a flow chart of a resource treatment method for acidic gases in incineration flue gas in embodiment 2 of the invention.
Description of the sequence numbers: SO 13An absorption tower, 2 heat exchangers, 3 a first-stage HCl absorption tower, 4 a second-stage HCl absorption tower, 5 a third-stage HCl absorption tower and 6 SO2Absorption tower, 7. sodium sulfite separator, 8. chimney
A: flue gas treated by a quench tower and a bag-type dust collector, B: recovering sulfuric acid, C: recovering hydrochloric acid, D: sodium sulfite solution, E: sodium sulfite, F: mother liquor, G: the flue gas discharged after reaching the standard.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A resource treatment method for acid gas in incineration flue gas comprises the following steps:
the flue gas with high content of oxysulfide and low content of hydrogen chloride generated by coal enters a flue gas absorption system after passing through a quench tower and a bag-type dust collector, and the flow rate of the flue gas is about 5000m before entering the absorption system3The temperature of the flue gas is 150-170 ℃;
the flue gas enters SO3The temperature of the absorption tower is 75-85 ℃, and SO is3The absorption tower takes water as an absorption medium, the recovered sulfuric acid is yellowish liquid, the concentration is 68%, and the content of the recovered HCl is 0.38%;
will pass through SO3The flue gas treated by the absorption tower enters a secondary HCl absorption tower for treatment, the HCl absorption tower takes water as an absorption medium, the HCl absorption tower adopts two-stage absorption, the recovered hydrochloric acid is moved out of the primary HCl absorption tower, the recovered hydrochloric acid is colorless transparent liquid, the concentration of the recovered hydrochloric acid is 24.6 percent, after the absorption liquid of the primary HCl absorption tower is recovered, the secondary absorption liquid is transferred to the primary, and the secondary supplements new water;
the flue gas is treated by an HCl absorption tower and then passes through SO2Absorption column, SO2The absorption tower adopts sodium hydroxide solution as absorption medium, the obtained solution containing sodium sulfite is treated to obtain sodium sulfite, and the residual mother liquor is filtered to supplement alkali and then is returned to SO2The absorption tower enters a wastewater treatment system after being reused for many times;
the purified flue gas is discharged into the atmosphere, and all indexes of the discharged flue gas are qualified
Example 2
A resource treatment method for acid gas in incineration flue gas is shown in figure 1 and comprises the following steps:
preparing the acid kettle residue with high sulfur and chlorine content generated in the chemical production process into uniform solution by using methanol, introducing the uniform solution into an incinerator for incineration, introducing the flue gas generated by incineration into a flue gas absorption system after passing through a quench tower and a bag-type dust collector, wherein the flow rate of the flue gas before entering the absorption system is about 5500m3The temperature of the flue gas is 150-170 ℃;
the flue gas enters SO3Absorption column, SO3The temperature of the absorption tower is 75-85 ℃, and SO3The absorption tower takes water as an absorption medium, the recovered sulfuric acid is yellowish liquid, the concentration is 72 percent, and the HCl content is 0.22 percent;
will pass through SO3The flue gas treated by the absorption tower enters a three-level HCl absorption tower for treatment, the HCl absorption tower takes water as an absorption medium, recovered hydrochloric acid is moved out of a first-level HCl absorption tower, the recovered hydrochloric acid is colorless transparent liquid, the concentration of the recovered hydrochloric acid is 21.3-25.5%, after the absorption liquid of the first-level HCl absorption tower is recovered, a second-level absorption liquid is transferred to the first level, a third-level absorption liquid is transferred to the second level, and new water is supplemented in the third level;
the flue gas is treated by an HCl absorption tower and then passes through SO2Absorption column, SO2The absorption tower adopts sodium carbonate solution as absorption medium to absorb SO2Adding a proper amount of sulfur into the solution containing sodium sulfite removed from the absorption tower, heating to 90-95 ℃, stirring for 1 hour, filtering to obtain sodium thiosulfate pentahydrate, filtering the mother liquor, supplementing alkali, and returning SO2The absorption tower enters a wastewater treatment system after being reused for many times;
the purified flue gas is discharged into the atmosphere, and all indexes of the discharged flue gas are qualified.
Example 3
The flue gas with high hydrogen chloride content and low sulfur oxide content generated by fuel oil enters a flue gas absorption system after passing through a quench tower and a bag-type dust collector, and the flow rate of the flue gas is about 4000m before entering the absorption system3The temperature of the flue gas is 150-170 ℃;
the flue gas enters SO3Absorption column, SO3The temperature of the absorption tower is 75-85 ℃, and SO3The absorption tower takes water as an absorption medium, the recovered sulfuric acid is yellowish liquid, the concentration is 67%, and the HCl content is 0.41%;
will pass through SO3The flue gas treated by the absorption tower enters a four-stage HCl absorption tower for treatment, the HCl absorption tower takes water as an absorption medium, recovered hydrochloric acid is moved out from a first-stage HCl absorption tower, the recovered hydrochloric acid is colorless transparent liquid, the concentration of the recovered hydrochloric acid is 21.6-24.7%, after the absorption liquid of the first-stage HCl absorption tower is recovered, a second-stage absorption liquid is transferred to the first stage, a third-stage absorption liquid is transferred to the second stage, a fourth-stage absorption liquid is transferred to the third stage, and the fourth stage is supplemented with new water;
the flue gas is treated by an HCl absorption tower and then passes through SO2Absorption column, SO2The absorption tower adopts sodium bicarbonate solution as absorption medium, SO2The solution containing sodium sulfite obtained from the absorption tower is treated to obtain sodium sulfite, and the residual mother liquor is supplemented with alkali and returned to SO2The absorption tower enters a wastewater treatment system after being reused for many times;
the purified flue gas is discharged into the atmosphere, and all indexes of the discharged flue gas are qualified.
Example 4
Introducing high-chlorine-content acidic wastewater generated in the chemical production process, activated carbon adsorbed with sulfur-containing organic matters and solid garbage into an incinerator for incineration, introducing flue gas generated by incineration into a flue gas absorption system after passing through a quench tower and a bag-type dust collector, wherein the flow rate of the flue gas before entering the absorption system is about 4000m3The temperature of the flue gas is 150-170 ℃;
the flue gas enters SO3Absorption column, SO3The temperature of the absorption tower is 75-85 ℃, and SO3The absorption tower takes water as an absorption medium. The recovered sulfuric acid is yellowish liquid with the concentration of71 percent and the HCl content is 0.25 percent;
will pass through SO3The flue gas treated by the absorption tower enters a four-stage HCl absorption tower for treatment, the HCl absorption tower takes water as an absorption medium, recovered hydrochloric acid is moved out of a first-stage HCl absorption tower, the recovered hydrochloric acid is colorless transparent liquid, the concentration of the recovered hydrochloric acid is 21.3-25.2%, after the absorption liquid of the first-stage HCl absorption tower is recovered, a second-stage absorption liquid is transferred to the first stage, a third-stage absorption liquid is transferred to the second stage, a fourth-stage absorption liquid is transferred to the third stage, and the fourth stage is supplemented with new water;
the flue gas is treated by an HCl absorption tower and then passes through SO2Absorption column, SO2The absorption tower adopts sodium bicarbonate solution as absorption medium, SO2The solution containing sodium sulfite obtained from the absorption tower is treated to obtain sodium sulfite, and the residual mother liquor is supplemented with alkali and returned to SO2The absorption tower enters a wastewater treatment system after being reused for many times;
the purified flue gas is discharged into the atmosphere, and all indexes of the discharged flue gas are qualified.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. A resource treatment method for acid gas in incineration flue gas is characterized by comprising the following steps:
(1) the incineration flue gas is sequentially subjected to cooling and filtering dust removal pretreatment;
(2) by SO3The absorption tower is used for absorbing SO in the pretreated flue gas3Carrying out an absorption treatment, the SO3A heat exchanger is arranged in the absorption tower to ensure that the absorption temperature is 75-90 ℃;
(3) via SO3Continuously feeding the flue gas treated by the absorption tower into a multistage HCl absorption tower to absorb HCl gas in the flue gas;
(4) smoke treated by HCl absorption towerGas enters SO2An absorption tower for absorbing SO in the flue gas2A gas;
(5) via SO2The flue gas absorbed by the absorption tower is introduced into a chimney and is discharged into the atmosphere.
2. The method according to claim 1, wherein the incineration flue gas in the step (1) comprises flue gas generated in the incineration process of waste, coal and fuel oil, or one of incineration flue gas generated in a thermal power plant and a coke-oven plant and other sulfur and chlorine-containing acidic incineration flue gas.
3. The method for recycling acid gases in incineration flue gas according to claim 1, wherein the pretreatment in step (1) is to pretreat the flue gas by a quenching tower and a bag-type dust remover.
4. The method according to claim 1, wherein the SO is used for recycling acid gases in incineration flue gas3The absorption tower takes water as an absorption medium, the sulfuric acid in the absorption tower is removed and new water is supplemented when the concentration reaches a certain concentration, and the concentration of the sulfuric acid in the removal of the sulfuric acid is 50-90%.
5. The method for recycling acid gases in incineration flue gas according to claim 4, wherein the concentration of the sulfuric acid removed is 65% -75%.
6. The method for recycling acid gases in incineration flue gas according to claim 1, wherein the HCl absorption towers all use water as an absorption medium, and the absorption stages of the multistage HCl absorption tower are 1-10 stages.
7. The resource treatment method of the acid gas in the incineration flue gas as claimed in claim 6, wherein the absorption stages of the multistage HCl absorption tower are 2-5 stages.
8. The method for recycling acid gases in incineration flue gas according to claim 1, wherein the flue gas passes through multiple stages of HCl absorption towers, the flue gas is removed when the concentration of hydrochloric acid in the first stage of HCl absorption tower reaches 15% -35%, the HCl in the next stage of HCl absorption tower is absorbed and transferred to the HCl in the previous stage of HCl absorption tower, and the HCl in the last stage of absorption tower is supplemented with fresh water.
9. The method according to claim 1, wherein the SO is used for recycling acid gases in incineration flue gas2The absorption liquid in the absorption tower is alkali liquor, and the alkali liquor is one of sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution.
10. The method according to claim 9, wherein the SO is used for recycling acid gases in incineration flue gas2Absorbing liquid in the absorption tower is removed after saturation, the removed absorbing liquid is treated to obtain sodium sulfite and mother liquor, and the mother liquor is filtered and then returns to SO2The absorption tower is used as an absorption liquid.
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