CN101757845A - Method for treating sulphur dioxide flue gas - Google Patents
Method for treating sulphur dioxide flue gas Download PDFInfo
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- CN101757845A CN101757845A CN200810234384A CN200810234384A CN101757845A CN 101757845 A CN101757845 A CN 101757845A CN 200810234384 A CN200810234384 A CN 200810234384A CN 200810234384 A CN200810234384 A CN 200810234384A CN 101757845 A CN101757845 A CN 101757845A
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Abstract
The invention particularly relates to a method for treating sulphur dioxide flue gas, which belongs to the technical field of environmental protection and is realized by the following procedures of: an absorption procedure: flue gas containing sulfur enters an absorption tower and is absorbed by a sodium hydroxide solution of 10% to 35% (wt); a decomposition procedure: the mixed solution reacts with hydrogen chloride gas and a sodium bisulfite solution is used for washing; a purification procedure: the sodium hydroxide solution is firstly added, sodium carbonate is then added and finally barium chloride is added; an electrolysis procedure: the sodium chloride solution is electrolyzed by a diaphragm method or an ion exchange membrane method; and a hydrogen chloride procedure: hydrogen and chlorine generated in the electrolysis procedure react in a reaction furnace to generate hydrogen chloride which is subjected to the decomposition procedure again. The method can be continuously and stably operated without factors of scaling, blockage, short-period replacement of material and equipment and the like; and a desulfurization system has good economy per se or the whole system has better economy after the desulfurization system is installed.
Description
Technical field: the invention belongs to environmental protection technical field, be specifically related to utilize sodium chloride to administer the method that contains sulfur dioxide flue gas and production high concentration sulfur dioxide.
Background technology: technology related to the present invention mainly contains both at home and abroad at present:
1. in low concentration sulphur dioxide flue gas reclaims technology, the soda method of one of at present industrial most widely used method, this method is strong to flue gas concentration adaptability, and tail gas reaches environmental requirement easily.Absorbing the sulfur dioxide afterproduct is sodium sulfite and sodium hydrogensulfite, this product characteristics instability, purposes is not extensive, if make high-concentration sulfur dioxide with sulfuric acid decomposition sodium sulfite and sodium hydrogensulfite, a large amount of metabisulfite solutions of by-product then, this product using value is not high; Produce sulfur dioxide if adopt steam heated to decompose, then steam consumption is big, and is less economical.
2. introduced the persulfuric acid oxidizing process in " the external sulfuric acid industry technical research report " that " sulfuric acid industry " editorial office 1985 publishes and removed and reclaim sulfur dioxide in flue gas, this method can make and finally enter atmosphere, middle sulfur dioxide concentration≤50ppm.But what this method reclaimed the production of sulphur resource also is the not high 30-40% dilute sulfuric acid of using value.
3.CN1012854, the removal methods of low-concentration sulfur dioxide in the flue gas, this method absorbs sulfur in smoke gas with basic aluminium sulphate solution.This method is at SO
2When concentration is lower than 2350ppm, less economical; At SO
2Concentration was greater than 1% o'clock, and tail gas is difficult to satisfy emission request.This method has the not high gypsum of a small amount of sulfur value to pay product in producing simultaneously.
4.CN1165051, a kind of high efficiency flue gas desulfurization technology, this method is utilized the sulfur dioxide in the NaOH absorption gas, generates sodium hydrogensulfite, and then utilizes calcium hydroxide regeneration, regenerates NaOH and recycles.This method does not reclaim the sulphur resource in the flue gas, produces a large amount of calcium sulfites, needs huge slag tip or landfill pond, can cause secondary pollution.Owing to absorbent NaOH is to be come by calcium hydroxide regeneration, introduce a large amount of Ca
2+, make the calcium knot easily takes place in the absorption equipment, influence system-wide continous-stable operation.
5.CN1066225 furfural dregs activated carbon and be used for eliminating and reclaim sulfur dioxide in flue gas adopts this kind activated carbon can eliminate the pollution of sulfur dioxide to atmosphere.What but this method reclaimed the production of sulphur resource is 30% not high left and right sides dilute sulfuric acid of using value.In addition, when sulfur dioxide concentration surpassed 7000-8000ppm, the concentration of sulfur dioxide also increased in the emptying end gas, is difficult to reach environmental requirement.
From above major technique related to the present invention, it is strong to sulfur dioxide in flue gas concentration adaptability also not exist a kind of method can possess such several characteristics: a. simultaneously at present, and tail gas reaches environmental requirement easily, does not produce secondary pollution.B. the sulphur resource in the flue gas can be fully recycled, and produces to be worth the raw material of industry product high, that purposes is wide.C. technology can continous-stable operation, do not exist such as fouling, obstruction and short period factor such as conversion materials and equipment more.D. the capable better economy of total system tool after desulphurization system itself has good and economic or gone up desulphurization system.
Summary of the invention: the purpose of this invention is to provide a kind of sodium chloride that utilizes that combines above each characteristics and administer the method for the flue gas and the production high concentration sulfur dioxide that contain sulfur dioxide.
The inventive method realizes by following operation:
1. absorption operation.Low-concentration sulfur dioxide gases such as the flue gas that the sulfurous fuels burning produces, sulfuric-acid production tail gas, flue gas during smelting are handled through purifying, lowering the temperature, enter the absorption tower that absorbs operation after removing dust, sulfur trioxide and acid mist wherein, sodium hydroxide solution with 10-35% (WT) absorbs down at 30-85 ℃, absorb back sulfur dioxide in flue gas content≤20～300ppm (volume), qualified discharge.NaOH and sulfur dioxide in the absorbent react, and liquid gas volume ratio is 1-10L/m in tower
3, gas-operated speed 0.6-2m/s in the absorption tower.
2. decomposition process.The hydrogen chloride gas that sodium sulfite that the absorption operation generates and sodium hydrogensulfite mixed solution and temperature are 120～180 ℃ reacts, contain sulfur dioxide, hydrogen chloride, steam and hydrogen in the reacted gas phase, a small amount of hydrogen chloride wherein is that the extension product of raw material is influential to the deep processing of sulfur dioxide gas with it, must be removed.Solution of sodium bisulfite with 25-38% (wt) among the present invention washs.Gas reusing fiber mist eliminator place to go salt acid mist and saline solution wherein after the washing finally makes the sulfur dioxide gas of chlorinity≤1.2mg/L concentration 〉=97%, can be directly as producing sulfur dioxide liquid or producing the raw material of sulfuric acid.
3. cleaning procedure.In the solution that decomposition process generates a large amount of sodium chloride, sulfur dioxide and a spot of Ca are arranged
2+, Mg
2+And SO
4 2-Ion in order to satisfy the needs of subsequent handling electrolysis, need carry out the adjusting with the pH value of removing of ion.Solution is added by desorption tower top, and pure air feeds liquid-gas ratio 1～100L/m by the desorption tower bottom
3, through take off inhale after the content≤0.1g/L of sulfur dioxide in the solution, take off the import that the humid gas that contains sulfur dioxide after the suction goes to absorb the operation absorption tower.In taking off the solution of inhaling sulfur dioxide, add sodium hydroxide solution earlier, remove the Mg in the solution
2+, after the reaction, in solution, add sodium carbonate again, in solution, add barium chloride at last again, then solution is filtered, this is a primary purification.Primary purification is crossed cleaner liquid and is done the diaphragm electrolysis use; Adopt electrolysis with ion-exchange film, also need clear liquid is carried out double purification.In filtering precipitate, add hydrochloric acid,, obtain medicinal barium sulfate sediment filtration, washing, drying.
Solution sodium chloride-containing～24% (wt) behind primary purification, SO
4 2-≤ 5g/L, SO
2≤ 0.1g/L, Mg
2++ Ca
2+≤ 0.1mg/L.
Solution sodium chloride-containing～24% (wt) behind double purification, SO
4 2-≤ 5g/L, SO
2≤ 0.1g/L, Mg
2++ Ca
2+≤ 20 μ g/L, solid suspension≤0.1ppm, Ba
2+≤ 1ppm.
4. electrowinning process.Sodium chloride solution after purifying is adopted diaphragm process or ion exchange membrane electrolysis, react in the electrolytic cell.Since adopt electrolytic method different, sodium hydrate content 10-35% in the solution after the electrolysis, temperature 70-95 ℃, as the absorbent that absorbs operation.Because requiring hydrogen and chlorine volume ratio when subsequent handling is made hydrogen chloride is 1.05-1.1, when just requiring electrolysis, this wants the sodium chloride of many electrolysis 5～10%, and the chlorine of unnecessary 5-10% is made clorox with the NaOH reactions that generate more.
5. hydrogen chloride operation.The hydrogen and the chlorine that utilize electrowinning process to produce react in reacting furnace than 1.05～1.1 (volumes) by hydrogen and chlorine, and the hydrogen chloride of generation is cooled to 120～180 ℃ through heat exchanger, removes decomposition process.
The specific embodiment: the present invention is described in detail below in conjunction with embodiment.
Embodiment:
Present embodiment uses the inventive method to handle the flue gas that contains secondary development sulfur oxide 3000ppm (volume) that coal-burning boiler produces, tolerance 600,000 Nm
3/ h, gas is sent into the absorption tower by blower fan after the processing that purifies, lowers the temperature, carry 35% sodium hydroxide solution 9m earlier with pump
3/ h absorbs, and utilizes the absorption liquid circulation to absorb internal circulating load 600m by pump again
3/ h absorbs back sulfur dioxide in flue gas content≤150ppm (volume), qualified discharge.The sodium sulfite and the sodium hydrogensulfite that absorb the back generation enter circulating slot, excess liquid overflows to the hydrogen chloride purifying tower in the circulating slot, flow into circulating slot then, the decomposition tower of carrying through pump reacts with the hydrogen chloride gas of temperature 120-180 ℃ of hydrogen 1-2% (volume).Excess liquid overflows to desorption tower in the circulating slot, takes off the import that the humid gas that contains sulfur dioxide after the suction removes blower fan, and the solution that takes off after the suction enters liquidceiver, overflows to clarifier-tank by liquidceiver again, and the underflow of clarifier-tank removes to produce barium sulfate.
Adopt electrolysis with ion-exchange film, by clear liquid is carried out double purification, and then deliver to electrolytic cell, the electrolytic sodium chloride power consumption is one ton of about 2200KW of sulfur dioxide power consumption of every production.The concentration of sodium hydroxide solution 35% that produces in the electrolytic cell goes to the absorption tower by the pump conveying, and wherein sub-fraction removes to make clorox.Hydrogen that produces in the electrolytic cell and chlorine react in reacting furnace by 1.05～1.1 (volumes) and generate hydrogen chloride, and hydrogen chloride removes decomposition tower behind heat exchanger, emit concentration greater than 97% sulfur dioxide 4886kg/h from scrubbing tower.
The inventive method can continous-stable operation, do not exist such as fouling, obstruction and short period factor such as conversion materials and equipment more: total system had better economy after desulphurization system itself had good and economic or gone up desulphurization system.Be applicable to low-concentration sulfur dioxide gases such as flue gas that sulfurous fuels burning produces, sulfuric-acid production tail gas, flue gas during smelting, content of sulfur dioxide 500ppm to 5% (volume) all can handle in the gas, strong to sulfur dioxide in flue gas concentration adaptability, tail gas reaches environmental requirement easily, does not produce secondary pollution; Sulphur resource in the flue gas can be fully recycled, and can produce to be worth the raw material of industry sulfur dioxide product high, that purposes is wide.
Claims (1)
1. method of administering sulfur dioxide flue gas, mainly utilize sodium chloride to administer the method for the flue gas and the production high concentration sulfur dioxide that contain sulfur dioxide, it is characterized in that this method realizes by following operation: absorb operation: the flue gas that the sulfurous fuels burning produces, sulfuric-acid production tail gas, low-concentration sulfur dioxide gases such as flue gas during smelting are through purifying, cooling is handled, remove dust wherein, enter the absorption tower behind sulfur trioxide and the acid mist, sodium hydroxide solution with 10-35% (WT) absorbs down at 30-85 ℃, absorb back sulfur dioxide in flue gas content≤20～300ppm (volume), qualified discharge, NaOH and sulfur dioxide in the absorbent react, and liquid gas volume ratio is 1-10L/m in tower
3, gas-operated speed 0.6-2m/s in the absorption tower; Decomposition process: the hydrogen chloride gas that sodium sulfite that the absorption operation generates and sodium hydrogensulfite mixed solution and temperature are 120～180 ℃ reacts, contain sulfur dioxide, hydrogen chloride, steam and hydrogen in the reacted gas phase, a small amount of hydrogen chloride wherein is that the extension product of raw material is influential to the deep processing of sulfur dioxide gas with it, must be removed, be washed with the solution of sodium bisulfite of 25-38% (wt).Gas reusing fiber mist eliminator place to go salt acid mist and saline solution wherein after the washing finally makes the sulfur dioxide gas of chlorinity≤1.2mg/L concentration 〉=97%, can be directly as producing sulfur dioxide liquid or producing the raw material of sulfuric acid; Cleaning procedure: in the solution that decomposition process generates a large amount of sodium chloride, sulfur dioxide and a spot of Ca are arranged
2+, Mg
2+And SO
4 2-Ion in order to satisfy the needs of subsequent handling electrolysis, need carry out the adjusting with the pH value of removing of ion, and solution is added by desorption tower top, and pure air feeds liquid-gas ratio 1～100L/m by the desorption tower bottom
3, through taking off the content≤0.1g/L that inhales sulfur dioxide in the solution of back, taking off the import that the humid gas that contains sulfur dioxide after the suction goes to absorb the operation absorption tower, adding sodium hydroxide solution earlier in taking off the solution of inhaling sulfur dioxide removes the Mg in the solution
2+, after the reaction, in solution, add sodium carbonate again, in solution, add barium chloride at last again, then solution is filtered, this is a primary purification, primary purification is crossed cleaner liquid and is done the diaphragm electrolysis use; Adopt electrolysis with ion-exchange film, also need clear liquid is carried out double purification, in filtering precipitate, add hydrochloric acid,, obtain medicinal barium sulfate sediment filtration, washing, drying; Solution sodium chloride-containing～24% (wt) behind primary purification, SO
4 2-≤ 5g/L, SO
2≤ 0.1g/L, Mg
2++ Ca
2+≤ 0.1mg/L, solution sodium chloride-containing～24% (wt) behind double purification, SO
4 2-≤ 5g/L, SO
2≤ 0.1g/L, Mg
2++ Ca
2+≤ 20 μ g/L, solid suspension≤0.1ppm, Ba
2+≤ 1ppm; Electrowinning process: the sodium chloride solution after will purifying adopts diaphragm process or ion exchange membrane electrolysis, react in the electrolytic cell, sodium hydrate content 10-35% in the solution after the electrolysis, temperature 70-95 ℃, as the absorbent that absorbs operation, because requiring hydrogen and chlorine volume ratio when subsequent handling is made hydrogen chloride is 1.05-1.1, when just requiring electrolysis, this wants the sodium chloride of many electrolysis 5～10%, and the chlorine of unnecessary 5-10% is made clorox with the NaOH reactions that generate more; The hydrogen chloride operation: the hydrogen and the chlorine that utilize electrowinning process to produce, in reacting furnace, react than 1.05～1.1 (volumes) by hydrogen and chlorine, the hydrogen chloride of generation is cooled to 120～180 ℃ through heat exchanger, returns decomposition process.
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|---|---|---|---|---|
| CN102583452A (en) * | 2011-01-07 | 2012-07-18 | 北京柯兰富尔过滤技术有限公司 | Method and equipment for directly producing sodium sulfite by using sulfuric acid-containing gas |
| CN104743727A (en) * | 2015-03-27 | 2015-07-01 | 山东大学 | System and method for cooperatively removing mercury with desulfurization waste water |
| CN106006881A (en) * | 2016-06-21 | 2016-10-12 | 首钢京唐钢铁联合有限责任公司 | Method and device for preparing bactericide |
| CN109485072A (en) * | 2018-12-18 | 2019-03-19 | 攀枝花钢企欣宇化工有限公司 | The integrated conduct method of form waste gas of sulfur dioxide |
| CN110639337A (en) * | 2019-11-01 | 2020-01-03 | 武汉青江化工黄冈有限公司 | SO based on sulphuric acid apparatus for producing2Wet gas extraction process |
| CN112794282A (en) * | 2021-02-06 | 2021-05-14 | 西安热工研究院有限公司 | System and method for producing hydrogen by using sulfur-containing flue gas of boiler |
| CN113941227A (en) * | 2021-11-26 | 2022-01-18 | 西安西热水务环保有限公司 | Method and system for selectively removing HCl in flue gas |
| CN114452788A (en) * | 2022-03-17 | 2022-05-10 | 江苏桂铭机械有限公司 | Sweetener with tail end detects |
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| CN102583452A (en) * | 2011-01-07 | 2012-07-18 | 北京柯兰富尔过滤技术有限公司 | Method and equipment for directly producing sodium sulfite by using sulfuric acid-containing gas |
| CN104743727A (en) * | 2015-03-27 | 2015-07-01 | 山东大学 | System and method for cooperatively removing mercury with desulfurization waste water |
| CN104743727B (en) * | 2015-03-27 | 2017-06-06 | 山东大学 | A kind of desulfurization wastewater cooperates with the System and method for of demercuration |
| CN106006881A (en) * | 2016-06-21 | 2016-10-12 | 首钢京唐钢铁联合有限责任公司 | Method and device for preparing bactericide |
| CN109485072A (en) * | 2018-12-18 | 2019-03-19 | 攀枝花钢企欣宇化工有限公司 | The integrated conduct method of form waste gas of sulfur dioxide |
| CN110639337A (en) * | 2019-11-01 | 2020-01-03 | 武汉青江化工黄冈有限公司 | SO based on sulphuric acid apparatus for producing2Wet gas extraction process |
| CN110639337B (en) * | 2019-11-01 | 2024-03-26 | 武汉青江化工黄冈有限公司 | SO based on sulfuric acid apparatus for producing 2 Wet gas extraction process |
| CN112794282A (en) * | 2021-02-06 | 2021-05-14 | 西安热工研究院有限公司 | System and method for producing hydrogen by using sulfur-containing flue gas of boiler |
| CN113941227A (en) * | 2021-11-26 | 2022-01-18 | 西安西热水务环保有限公司 | Method and system for selectively removing HCl in flue gas |
| CN114452788A (en) * | 2022-03-17 | 2022-05-10 | 江苏桂铭机械有限公司 | Sweetener with tail end detects |
| CN115108916A (en) * | 2022-07-19 | 2022-09-27 | 胡士国 | Preparation method of trichloronitromethane |
| CN115108916B (en) * | 2022-07-19 | 2024-05-28 | 胡士国 | Preparation method of trichloronitromethane |
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Open date: 20100630 |