CN102266713B - Absorption method for producing chlorine-containing gas by electrolyzing fused salt - Google Patents
Absorption method for producing chlorine-containing gas by electrolyzing fused salt Download PDFInfo
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- CN102266713B CN102266713B CN 201110140778 CN201110140778A CN102266713B CN 102266713 B CN102266713 B CN 102266713B CN 201110140778 CN201110140778 CN 201110140778 CN 201110140778 A CN201110140778 A CN 201110140778A CN 102266713 B CN102266713 B CN 102266713B
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Abstract
The invention relates to an absorption method for producing chlorine-containing gas by electrolyzing fused salt. The method comprises the following steps of: (1) connecting a gas inlet tube in an absorption device with a gas outlet main tube above a fused salt electrolysis tank, and connecting the gas outlet main tube with each gas outlet branch tube above each electrolysis tank; (2) supplying a sodium hydroxide solution into a cleaning tower and an absorption tower respectively from a sodium hydroxide storage tank; (3) opening a control valve II and liquid supply pumps II and III so that the liquid in the bottoms of the cleaning tower and the absorption tower is sprayed into the towers and flows back into the bottoms of the towers to be circulated; (4) opening an air volume adjusting valve and an air blower, and then opening the electrolysis tank; (5) mixing the chlorine-containing gas generated in the electrolysis process with a part of cold air and the sodium hydroxide solution; (6) supplying the cleaned and cooled gas into the absorption tower to mix with the sodium hydroxide solution so that the chlorine gas in the gas is absorbed, and the liquid drops carried in the gas removing chlorine gas are separated; and (7) exhausting the gas. The method provided by the invention can effectively treat high-temperature chlorine-containing exhaust gas containing components such as water vapor, hydrogen chloride and the like.
Description
Technical field
The present invention relates to chemical technology field, relate in particular to a kind of absorption process of chlorine-bearing gas generated in molten salt electrolysis.
Background technology
At present, meeting by-product chlorine or chloride tail gas, for the processing of these chlorine or chloride tail gas, according to the amount of the chlorine-containing gas that produces and the difference of composition, can adopt different processing methods in electrolytic industry and other industrial production.If the amount of chlorine that produces is large and purity is higher, can prepare liquid chlorine; If the amount of chlorine that produces is little and purity is lower, can consider to absorb the preparation ferric chloride solution with solution of ferrous chloride, perhaps absorb preparation liquor natrii hypochloritis etc. with sodium hydroxide solution.Sometimes the chlorine temperature that electrolysis produces is higher, and contain other composition, such as, during take moisture chloride as primary raw material electrolytic preparation metal simple-substance and metal alloy, the gas temperature that electrolysis produces is higher, and contain water vapour, hydrogen chloride etc., and the processing of the chlorine-containing gas that at this moment electrolysis is produced is improper with usual way, and perhaps treatment effect is bad.In this case, the processing of chlorine-containing gas needed special consideration.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of effective processing high temperature and contains water vapour and the absorption process of the chlorine-bearing gas generated in molten salt electrolysis of the composition such as hydrogen chloride.
For addressing the above problem, the absorption process of chlorine-bearing gas generated in molten salt electrolysis of the present invention comprises the following steps:
(1) exhaust main with the air inlet pipe in the absorption plant of chlorine-bearing gas generated in molten salt electrolysis and fused-salt bath top is connected, and this exhaust main is connected with exhaust branch pipe above each electrolytic cell;
(2) sending into respectively mass concentration with infusion pump I in scrubbing tower, the absorption tower by the NaOH storage tank is that 15～45% sodium hydroxide solution to liquid level is 0.3～0.9m, then closes the control valve III on described infusion pump I and sodium hydroxide solution woven hose;
(3) open respectively with described scrubbing tower, absorption tower in supporting control valve II and infusion pump II, the infusion pump III of liquid-circulating, make at the liquid of described scrubbing tower and bottom, described absorption tower and sent into respectively top and the middle part on the top of described scrubbing tower, described absorption tower by described infusion pump II, infusion pump III, and be sprayed onto in tower, liquid circulates at the bottom of flowing to tower by self gravitation;
(4) volume damper is placed in 1/3rd and opens to fully open position, open blower fan, open electrolytic cell;
(5) chlorine-containing gas that produces in electrolytic process of described electrolytic cell is under the suction function that blower fan produces, enter exhaust main from the exhaust branch pipe that is configured in described electrolytic cell top, a part of cold air also enters described exhaust main simultaneously, and the chlorine-containing gas that electrolysis is produced is cooled; At this moment, mist enters described scrubbing tower by described exhaust main through air inlet pipe, mix with the sodium hydroxide solution in described scrubbing tower, make along with a small amount of hydrogen chloride gas that contains in the electrolyte of chlorine-containing gas volatilization and chlorine-containing gas is washed into or absorbs the feed liquor phase, gas obtains cooling; Simultaneously the material after described sodium hydroxide solution and chlorine-containing gas haptoreaction passes through infusion pump II and cooling after heat exchanger, again enters described scrubbing tower from described heat exchanger top;
(6) through washing and cooling gas under the negative pressure that described blower fan produces promotes, enter described absorption tower from described scrubbing tower, the sodium hydroxide solution that sprays with top, described absorption tower and middle part mixes, and the chlorine in gas is absorbed; At this moment, flow to sodium hydroxide solution at the bottom of tower and be recycled and deliver to top, described absorption tower and the middle part sprays continuously, the gas that has been absorbed chlorine is flowed out by top, described absorption tower, enters cyclone separator; Make the drop of carrying secretly in gas separated through described cyclone separator;
(7) be removed the gas of drop through being drained after described volume damper and described blower fan.
Electrolytic cell in described step (1) is open type.
Chlorine-containing gas in described step (5) is prepared by the chloride system molten-salt electrolysis in the process of metal simple-substance or alloy and produces; Wherein the electrolysis raw material is anhydrous chloride or moisture chloride.
In vent gas in described step (7), chlorine content is less than or equal to 3ppm; When in vent gas, chlorine content is higher than 3ppm, has configured the chlorine alarm near the emptying pipe outlet and sent alarm.
In described step (5) scrubbing tower in sodium hydroxide solution available chlorine content reach more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve IV, by infusion pump II, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passing into fresh mass concentration to described scrubbing tower is 15～45% sodium hydroxide solution.
In described step (6) absorption tower in sodium hydroxide solution available chlorine content reach more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve V, by infusion pump III, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passes into fresh mass concentration to described absorption tower and be 15～45% sodium hydroxide solution.
The present invention compared with prior art has the following advantages:
1, the air cooling system that consists of due to the house steward who has configured in the present invention after being joined by the exhaust branch pipe above electrolytic cell and arm, also be provided with scrubbing tower between exhaust main and absorption tower, therefore, the present invention both had been suitable for low temperature, be suitable for again the processing of the chloride water electrolytic gas of high temperature, be particularly suitable for high temperature and contain the processing of steam, hydrogen chloride, the electrolytical chloride water electrolytic gas of volatilization.
2, the configuration due to electrolytic cell top exhaust branch pipe in the present invention has taken into full account different feed way, and therefore, the present invention both had been suitable for carrying out take anhydrous chloride as raw material the situation of electrolysis, was suitable for again carrying out take moisture chloride as raw material the situation of electrolysis.
3, technological process of the present invention is short, easy to operate.
The specific embodiment
When embodiment 1 utilized anhydrous or moisture lanthanum chloride for primary raw material list groove electrolytic preparation lanthanoid metal, the molten-salt electrolysis system that adopts was KCl-LaCl
3System, Faradaic current 1000～2000A, 800～1000 ℃ of electrolysis temperatures, single groove electrolysis per hour produces chlorine 2～4kg.Adopting anhydrous lanthanum chloride is raw material when carrying out electrolysis, mainly contains chlorine in the gas that electrolysis produces; Adopting moisture lanthanum chloride is raw material when carrying out electrolysis, except containing chlorine, also contains a small amount of steam and hydrogen chloride in the gas that electrolysis produces.
The absorption process of chlorine-bearing gas generated in molten salt electrolysis comprises the following steps:
(1) air inlet pipe in the absorption plant of chlorine-bearing gas generated in molten salt electrolysis (by Qinghai Yanhu Inst., Chinese Academy of Sciences's development) is connected with the exhaust main of fused-salt bath top, this exhaust main is connected with exhaust branch pipe above each electrolytic cell.
(2) sending into respectively mass concentration with infusion pump I in scrubbing tower, the absorption tower by the NaOH storage tank is that 15～35% sodium hydroxide solution to liquid level is 0.3～0.9m, then closes the control valve III on infusion pump I and sodium hydroxide solution woven hose.
(3) open respectively with scrubbing tower, absorption tower in supporting control valve II and infusion pump II, the infusion pump III of liquid-circulating, make at the liquid of scrubbing tower and bottom, described absorption tower and sent into respectively the top of scrubbing tower, top and the middle part on absorption tower by infusion pump II, infusion pump III, and be sprayed onto in tower, liquid circulates at the bottom of flowing to tower by self gravitation.
(4) volume damper is placed in 1/3rd positions of opening, opens blower fan, open electrolytic cell.
(5) chlorine-containing gas that produces in electrolytic process of electrolytic cell is under the suction function that blower fan produces, enter exhaust main from the exhaust branch pipe that is configured in electrolytic cell top, a part of cold air also enters exhaust main simultaneously, and the chlorine-containing gas that electrolysis is produced is cooled; At this moment, mist enters scrubbing tower by exhaust main through air inlet pipe, mix with the sodium hydroxide solution in scrubbing tower, make along with a small amount of hydrogen chloride gas that contains in the electrolyte of chlorine-containing gas volatilization and chlorine-containing gas is washed into or absorbs the feed liquor phase, gas obtains cooling; Simultaneously the material after sodium hydroxide solution and chlorine-containing gas haptoreaction passes through infusion pump II and cooling after heat exchanger, again enters scrubbing tower from the heat exchanger top.
When available chlorine content in sodium hydroxide solution in scrubbing tower reaches more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve IV, by infusion pump II, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passing into fresh mass concentration to scrubbing tower is 15～45% sodium hydroxide solution.
(6) through washing and cooling gas under the negative pressure that blower fan produces promotes, enter the absorption tower from scrubbing tower, the sodium hydroxide solution that sprays with top, absorption tower and middle part mixes, and the chlorine in gas is absorbed; At this moment, flow to sodium hydroxide solution at the bottom of tower and be recycled and deliver to the top, absorption tower and the middle part sprays continuously, the gas that has been absorbed chlorine is flowed out by the top, absorption tower, enters cyclone separator; Make the drop of carrying secretly in gas separated through cyclone separator.
When available chlorine content in sodium hydroxide solution in the absorption tower reaches more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve V, by infusion pump III, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passes into fresh mass concentration to the absorption tower and be 15～45% sodium hydroxide solution.
(7) be removed the gas of drop through being drained after volume damper and blower fan.
When embodiment 2 utilized anhydrous or moisture lanthanum chloride for primary raw material multiple-grooved electrolytic preparation lanthanoid metal, the molten-salt electrolysis system that adopts was KCl-LaCl
3System, single groove Faradaic current 1000～2000A, 800～1000 ℃ of electrolysis temperatures, single groove electrolysis per hour produces chlorine 2～4kg, and during 5 electrolytic cell electrolysis simultaneously, per hour common property is given birth to chlorine 10～20kg.
The absorption process of chlorine-bearing gas generated in molten salt electrolysis comprises the following steps:
(1) air inlet pipe in the absorption plant of chlorine-bearing gas generated in molten salt electrolysis (by Qinghai Yanhu Inst., Chinese Academy of Sciences's development) is connected with the exhaust main of fused-salt bath top, this exhaust main is connected with exhaust branch pipe above each electrolytic cell.
(2) sending into respectively mass concentration with infusion pump I in scrubbing tower, the absorption tower by the NaOH storage tank is that 35～45% sodium hydroxide solution to liquid level is 0.3～0.9m, then closes the control valve III on infusion pump I and sodium hydroxide solution woven hose.
(3) open respectively with scrubbing tower, absorption tower in supporting control valve II and infusion pump II, the infusion pump III of liquid-circulating, make at the liquid of scrubbing tower and bottom, described absorption tower and sent into respectively the top of scrubbing tower, top and the middle part on absorption tower by infusion pump II, infusion pump III, and be sprayed onto in tower, liquid circulates at the bottom of flowing to tower by self gravitation.
(4) volume damper is placed in the position of standard-sized sheet, opens blower fan, open electrolytic cell.
(5) chlorine-containing gas that produces in electrolytic process of electrolytic cell is under the suction function that blower fan produces, enter exhaust main from the exhaust branch pipe that is configured in electrolytic cell top, a part of cold air also enters exhaust main simultaneously, and the chlorine-containing gas that electrolysis is produced is cooled; At this moment, mist enters scrubbing tower by exhaust main through air inlet pipe, mix with the sodium hydroxide solution in scrubbing tower, make along with a small amount of hydrogen chloride gas that contains in the electrolyte of chlorine-containing gas volatilization and chlorine-containing gas is washed into or absorbs the feed liquor phase, gas obtains cooling; Simultaneously the material after sodium hydroxide solution and chlorine-containing gas haptoreaction passes through infusion pump II and cooling after heat exchanger, again enters scrubbing tower from the heat exchanger top.
When available chlorine content in sodium hydroxide solution in scrubbing tower reaches more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve IV, by infusion pump II, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passing into fresh mass concentration to scrubbing tower is 35～45% sodium hydroxide solution.
(6) through washing and cooling gas under the negative pressure that blower fan produces promotes, enter the absorption tower from scrubbing tower, the sodium hydroxide solution that sprays with top, absorption tower and middle part mixes, and the chlorine in gas is absorbed; At this moment, flow to sodium hydroxide solution at the bottom of tower and be recycled and deliver to the top, absorption tower and the middle part sprays continuously, the gas that has been absorbed chlorine is flowed out by the top, absorption tower, enters cyclone separator; Make the drop of carrying secretly in gas separated through cyclone separator.
When available chlorine content in sodium hydroxide solution in the absorption tower reaches more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve V, by infusion pump III, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passes into fresh mass concentration to the absorption tower and be 35～45% sodium hydroxide solution.
(7) be removed the gas of drop through being drained after volume damper and blower fan.
When embodiment 3 utilized anhydrous chloride for primary raw material list groove electrolytic preparation magnesium-lanthanum alloy, the molten-salt electrolysis system that adopts was KCl-MgCl
2-LaCl
3System, single groove Faradaic current 1000～2000A, 800～1000 ℃ of electrolysis temperatures, single groove electrolysis per hour produces chlorine 2～4kg.Mainly contain chlorine in the gas that electrolysis produces.
The absorption process of chlorine-bearing gas generated in molten salt electrolysis is identical with embodiment 1, wherein volume damper be placed in two/-position of Kai.
When embodiment 4 utilized anhydrous chloride for primary raw material multiple-grooved electrolytic preparation magnesium-lanthanum alloy, the molten-salt electrolysis system that adopts was KCl-MgCl
2-LaCl
3System, single groove Faradaic current 1000～2000A, 800～1000 ℃ of electrolysis temperatures, single groove electrolysis per hour produces chlorine 2～4kg, and during 5 electrolytic cell electrolysis simultaneously, per hour common property is given birth to chlorine 10～20kg.Mainly contain chlorine in the gas that electrolysis produces.
The absorption process of chlorine-bearing gas generated in molten salt electrolysis is identical with embodiment 2.
When embodiment 5 utilized moisture chloride for primary raw material list groove electrolytic preparation magnesium-lanthanum alloy, the molten-salt electrolysis system that adopts was KCl-MgCl
2-LaCl
3System, single groove Faradaic current 1000～2000A, 800～1000 ℃ of electrolysis temperatures, single groove electrolysis per hour produces chlorine 2～4kg.Except containing chlorine, also contain steam and the hydrogen chloride of part in the gas that electrolysis produces.
The absorption process of chlorine-bearing gas generated in molten salt electrolysis is identical with embodiment 1.
When embodiment 6 utilized moisture chloride for primary raw material multiple-grooved electrolytic preparation magnesium-lanthanum alloy, the molten-salt electrolysis system that adopts was KCl-MgCl
2-LaCl
3System, single groove Faradaic current 1000～2000A, 800～1000 ℃ of electrolysis temperatures.Single groove electrolysis per hour produces chlorine 2～4kg, and during 5 electrolytic cell electrolysis simultaneously, per hour common property is given birth to chlorine 10～20kg.Except containing chlorine, also contain steam and the hydrogen chloride of part in the gas that electrolysis produces.
The absorption process of chlorine-bearing gas generated in molten salt electrolysis is identical with embodiment 2.
In above-described embodiment 1～6, electrolytic cell is open type; In vent gas in step (7), chlorine content is less than or equal to 3ppm; When in vent gas, chlorine content is higher than 3ppm, has configured the chlorine alarm near the emptying pipe outlet and sent alarm.
Claims (6)
1. the absorption process of chlorine-bearing gas generated in molten salt electrolysis comprises the following steps:
(1) exhaust main with the air inlet pipe in the absorption plant of chlorine-bearing gas generated in molten salt electrolysis and fused-salt bath top is connected, and this exhaust main is connected with exhaust branch pipe above each electrolytic cell;
(2) sending into respectively mass concentration with infusion pump I in scrubbing tower, the absorption tower by the NaOH storage tank is that 15～45% sodium hydroxide solution to liquid level is 0.3～0.9m, then closes the control valve III on described infusion pump I and sodium hydroxide solution woven hose;
(3) open respectively with described scrubbing tower, absorption tower in supporting control valve II and infusion pump II, the infusion pump III of liquid-circulating, make at the liquid of described scrubbing tower and bottom, described absorption tower and sent into respectively top and the middle part on the top of described scrubbing tower, described absorption tower by described infusion pump II, infusion pump III, and be sprayed onto in tower, liquid circulates at the bottom of flowing to tower by self gravitation;
(4) volume damper is placed in 1/3rd and opens to fully open position, open blower fan, open electrolytic cell;
(5) chlorine-containing gas that produces in electrolytic process of described electrolytic cell is under the suction function that blower fan produces, enter exhaust main from the exhaust branch pipe that is configured in described electrolytic cell top, a part of cold air also enters described exhaust main simultaneously, and the chlorine-containing gas that electrolysis is produced is cooled; At this moment, mist enters described scrubbing tower by described exhaust main through air inlet pipe, mix with the sodium hydroxide solution in described scrubbing tower, make along with a small amount of hydrogen chloride gas that contains in the electrolyte of chlorine-containing gas volatilization and chlorine-containing gas is washed into or absorbs the feed liquor phase, gas obtains cooling; Simultaneously the material after described sodium hydroxide solution and chlorine-containing gas haptoreaction passes through infusion pump II and cooling after heat exchanger, again enters described scrubbing tower from described heat exchanger top;
(6) through washing and cooling gas under the negative pressure that described blower fan produces promotes, enter described absorption tower from described scrubbing tower, the sodium hydroxide solution that sprays with top, described absorption tower and middle part mixes, and the chlorine in gas is absorbed; At this moment, flow to sodium hydroxide solution at the bottom of tower and be recycled and deliver to top, described absorption tower and the middle part sprays continuously, the gas that has been absorbed chlorine is flowed out by top, described absorption tower, enters cyclone separator; Make the drop of carrying secretly in gas separated through described cyclone separator;
(7) be removed the gas of drop through being drained after described volume damper and described blower fan.
2. the absorption process of chlorine-bearing gas generated in molten salt electrolysis as claimed in claim 1, it is characterized in that: the electrolytic cell in described step (1) is open type.
3. the absorption process of chlorine-bearing gas generated in molten salt electrolysis as claimed in claim 1 is characterized in that: the chlorine-containing gas in described step (5) is prepared by the chloride system molten-salt electrolysis in the process of metal simple-substance or alloy and produces; Wherein the electrolysis raw material is anhydrous chloride or moisture chloride.
4. the absorption process of chlorine-bearing gas generated in molten salt electrolysis as claimed in claim 1, it is characterized in that: in the vent gas in described step (7), chlorine content is less than or equal to 3ppm; When in vent gas, chlorine content is higher than 3ppm, has configured the chlorine alarm near the emptying pipe outlet and sent alarm.
5. the absorption process of chlorine-bearing gas generated in molten salt electrolysis as claimed in claim 1, it is characterized in that: in described step (5) scrubbing tower in sodium hydroxide solution available chlorine content reach more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve IV, by infusion pump II, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passing into fresh mass concentration to described scrubbing tower is 15～45% sodium hydroxide solution.
6. the absorption process of chlorine-bearing gas generated in molten salt electrolysis as claimed in claim 1, it is characterized in that: in described step (6) absorption tower in sodium hydroxide solution available chlorine content reach more than 5%, and the mol ratio of NaOH and clorox is 1: 2～1: 4 o'clock, open control valve V, by infusion pump III, the liquor natrii hypochloritis is input to liquor natrii hypochloritis's storage tank, then passes into fresh mass concentration to described absorption tower and be 15～45% sodium hydroxide solution.
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| CN 201110140778 CN102266713B (en) | 2011-05-25 | 2011-05-25 | Absorption method for producing chlorine-containing gas by electrolyzing fused salt |
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| CN 201110140778 CN102266713B (en) | 2011-05-25 | 2011-05-25 | Absorption method for producing chlorine-containing gas by electrolyzing fused salt |
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| CN102266713B true CN102266713B (en) | 2013-05-15 |
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| CN115888393A (en) * | 2023-01-09 | 2023-04-04 | 云南国钛金属股份有限公司 | Molten salt chlorinated chlorine absorption circulating system and method |
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| US20100316548A1 (en) * | 2009-06-10 | 2010-12-16 | Bullen Patrick J | Methods and systems for efficient neutralization of acid gases |
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