CN107190278A - A kind of processing method of chlorate in electrolytic cell light salt brine - Google Patents
A kind of processing method of chlorate in electrolytic cell light salt brine Download PDFInfo
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- CN107190278A CN107190278A CN201710353738.XA CN201710353738A CN107190278A CN 107190278 A CN107190278 A CN 107190278A CN 201710353738 A CN201710353738 A CN 201710353738A CN 107190278 A CN107190278 A CN 107190278A
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- light salt
- salt brine
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention provides a kind of processing method of the chlorate in electrolytic cell light salt brine, including：Organic acid is added into electrolytic cell light salt brine.Chlorate is decomposed into the chlorion, water and carbon dioxide of negative one valency by the present invention, while other materials in light salt brine are easy to implement, quickly, while efficiency is very high without interference with the reaction of organic acid.Chlorate is decomposed into the chlorion, water and carbon dioxide of negative one valency by using organic acid by the present invention, while other materials in light salt brine are easy to implement, quickly, while efficiency is very high without interference with the reaction of organic acid.
Description
Technical field
The present invention relates to water treatment agent field, more particularly, to a kind of place of the chlorate in electrolytic cell light salt brine
Reason method.
Background technology
The production method of current chlor-alkali caustic soda uses the technique of electrolysis with ion-exchange film sodium chloride brine mostly, the technique with from
The continuous decline of sub- film periodic performance, it may appear that chlorate content is constantly enriched with rise and exceeded situation in sodium chloride brine,
Chlorate is the inevitable outcome in electrolytic process, mainly from the anti-OH moved of negative electrode-With the chlorine reaction generation time of anode
Disproportionated reaction occurs again in anode chamber for chlorate, hypochlorite, generates chlorate.Generation speed and the current efficiency of chlorate have
Much relations, current efficiency is lower, from the anti-OH for adjourning anode of negative electrode-It is more.Chlorate content's height in salt solution will influence chlorine
Change the saturation degree of sodium；Simultaneously as operation reason, when the pH value of salt solution is less than 7, chlorate will release chlorine with HCl reactions,
Etching apparatus；Chlorate content in sodium chloride brine will influence the chlorate content in alkali, corrodes the pipeline of alkali system and sets
It is standby.
Traditional chlorate technique of removing uses the method that a large amount of hydrochloric acid are added in sodium chloride brine and are heated up with steam,
Under hot conditions, with chlorate the chlorate that chemical reaction is gone in demineralized water occurs for hydrochloric acid, and excessive hydrochloric acid is neutralized with alkali again, this
On the one hand plant traditional handicraft needs to consume substantial amounts of hydrochloric acid, steam and caustic soda, causes operating cost huge；On the other hand after reacting
A large amount of waste chlorines can be produced, causes potential safety hazard, or manufacture sodium hypochlorite, can also consume caustic soda.Sodium hypochlorite yield is caused to increase
Plus, once air guide, which can freely not forced, stops the whole chlor-alkali production system of waste gas absorbing system influence.
The content of the invention
The present invention is provided in a kind of electrolytic cell light salt brine for overcoming above mentioned problem or solving the above problems at least in part
Chlorate processing method.
According to an aspect of the present invention there is provided a kind of processing method of the chlorate in electrolytic cell light salt brine, including：To
Organic acid is added in electrolytic cell light salt brine.
Preferably, the present invention further comprises：
A part of light salt brine in electrolytic cell is drained in the first cell body, organic acid is added into first cell body；
Another part light salt brine in electrolytic cell is drained in the second cell body, when chlorate contains in first cell body
When amount is less than 2g/L, the light salt brine in first cell body is drained in the second cell body.
Preferably, the flow-rate ratio of light salt brine is 1 in first cell body and the second cell body:10-15.
Preferably, the flow-rate ratio of light salt brine is 1 in first cell body and the second cell body:13.5.
Preferably, the organic acid includes the one or more in formic acid, oxalic acid, tartaric acid, lactic acid and citric acid.
Preferably, the organic acid is one kind in lactic acid and citric acid.
Preferably, the mass fraction of the organic acid is 5%-30%.
Preferably, present invention additionally comprises：
The light salt brine that second cell body flows out is subjected to dechlorination processing, then added into the light salt brine handled by dechlorination
The pH of caustic soda to light salt brine is in alkalescence, and the light salt brine of alkalescence is carried out into engaging sulphate processing.
Preferably, the pH of the alkaline light salt brine is 10.
Preferably, the temperature of the electrolytic cell light salt brine is 85-88 DEG C.
The application proposes a kind of processing method of the chlorate in electrolytic cell light salt brine, by adding into electrolytic cell light salt brine
Enter organic acid, chlorate is decomposed into the chlorion, water and carbon dioxide of negative one valency, while other materials in light salt brine are not
The reaction of organic acid can be disturbed, is easy to implement, quickly, while efficiency is very high.Why the present invention does not use inorganic acid to decompose chlorine
Hydrochlorate, is due to that can increase the sulfate concentration of system with inorganic reducing agent, because the subsequent process of electrolytic sodium chloride is also present
The process of denitration, excessive sulfate radical can increase the cost of denitration.
Embodiment
With reference to embodiment, the embodiment to the present invention is described in further detail.Following examples are used for
Illustrate the present invention, but be not limited to the scope of the present invention.
Traditional chlorate technique of removing uses the method that a large amount of hydrochloric acid are added in sodium chloride brine and are heated up with steam,
Under hot conditions, with chlorate the chlorate that chemical reaction is gone in demineralized water occurs for hydrochloric acid, and excessive hydrochloric acid is neutralized with alkali again, this
On the one hand plant traditional handicraft needs to consume substantial amounts of hydrochloric acid, steam and caustic soda, causes operating cost huge；On the other hand after reacting
A large amount of waste chlorines can be produced, causes potential safety hazard, or manufacture sodium hypochlorite, can also consume caustic soda.Sodium hypochlorite yield is caused to increase
Plus, once air guide, which can freely not forced, stops the whole chlor-alkali production system of waste gas absorbing system influence.
In order to overcome above mentioned problem of the prior art, the present invention provides a kind of place of the chlorate in electrolytic cell light salt brine
Reason method, including：Organic acid is added into electrolytic cell light salt brine.
It should be noted that reacted by organic acid with chlorate, by chlorate be decomposed into negative one valency chlorion,
Water and carbon dioxide, while other materials in light salt brine are easy to implement, quickly, simultaneously without interference with the reaction of organic acid
Efficiency is very high.Why the present invention does not use inorganic acid to decompose chlorate, is due to that can increase the sulphur of system with inorganic reducing agent
Acid group concentration, because also there is the process of denitration in the subsequent process of electrolytic sodium chloride, excessive sulfate radical can increase denitration into
This.
In one alternate embodiment, the processing method of the chlorate in electrolytic cell light salt brine of the invention, is further wrapped
Include：
A part of light salt brine in electrolytic cell is drained in the first cell body, organic acid is added into the first cell body.
When a part of light salt brine in electrolytic cell is drained into the first cell body, while another part in electrolytic cell is light
Salt solution is drained in the second cell body, when the content of chlorate in the first cell body is less than 2g/L, by the light salt brine in the first cell body
It is drained in the second cell body.
It should be noted that in actual production, the flow of electrolytic cell light salt brine is very big, can be usually reached 250-
300m3/ h, if organic acid is directly poured into electrolytic cell, it is clear that the consumption of organic acid can be greatly improved, simultaneously because light
The flow of salt solution is excessive, and organic acid is difficult fully to be contacted with chlorate anions particle, and then reduces reaction efficiency, therefore, the present invention
By the way that a part of light salt brine in electrolytic cell is drained into the first cell body, only the chlorate in the first cell body is handled.
It should be noted that the light salt brine after the processing of the first cell body is mixed with the light salt brine in the second cell body, make
The content reduction of chlorate in light salt brine after mixing, also, due to the reaction of chlorate in the first cell body, chlorate
Content is necessarily fewer and fewer, and the reaction probabilities of organic acid and chlorate are also constantly reduced, unreacted organic acid in light salt brine,
After being mixed with the light salt brine in the second cell body, because the content of chlorate in light salt brine in the second cell body is very big, the first groove of script
Unreacted organic acid just can continue to react with the chlorate of light salt brine in the second cell body in body, make organic acid in the second cell body
In content it is almost depleted, enter without influenceing follow-up desulfurization process.
Through technical grade Experimental comparison, in the case of chlorate eliminates index identical, draw using by light salt brine in electrolytic cell
It flow to two cell bodies, and only adds the processing method (method 1) of organic acid in a cell body thereto and direct into electrolytic cell
The processing method (method 2) for adding organic acid is compared, and method 1 can save 5-10% organic acid, for industrial production,
With very high economic value.
In one alternate embodiment, the flow-rate ratio of light salt brine is 1 in the first cell body and the second cell body:10-15.
It should be noted that the flow of light salt brine is much smaller than the flow of light salt brine in the second cell body in the first cell body so that
Organic acid can fully react with the chlorate anions in the first cell body.
In an optimum embodiment, the flow-rate ratio of light salt brine is 1 in the first cell body and the second cell body:13.5.
In one alternate embodiment, the processing method of the chlorate in electrolytic cell light salt brine also includes：
The light salt brine that second cell body flows out is subjected to dechlorination processing, then added into the light salt brine handled by dechlorination
The pH of caustic soda to light salt brine is in alkalescence, and the light salt brine of alkalescence is carried out into engaging sulphate processing.
In one alternate embodiment, the temperature of the electrolytic cell light salt brine is 85-88 DEG C.
It should be noted that due to CO can be generated using organic acid and chloric acid reactant salt2, the water temperature of comprehensive electrolytic cell is
85-88 DEG C, CO2It is easy to escape into air from light salt brine after the reaction, the acidity of light salt brine can be reduced, after being conducive to
Continuous engaging sulphate process step.
In one alternate embodiment, organic acid includes one kind in formic acid, oxalic acid, tartaric acid, lactic acid and citric acid
Or it is a variety of.Above-mentioned organic acid is not acid strong, and the amount needed for being unlikely to corrosion pipeline, and reaction is relatively small, can save into
This.
Specifically, the chemical equation of each organic acid and chlorate is as follows：
The chemical equation of lactic acid and chlorate：
C3H6O3+2NaClO3=2NaCl+3H2O+3CO2
The chemical equation of Citric Acid Mono and chlorate：
C6H8O7+3NaClO3=3NaCl+4H2O+6CO2
The chemical equation of formic acid and chlorate：
3CH2O2+NaClO3=NaCl+3H2O+3CO2
The chemical equation of oxalic acid and chlorate：
3C2H4O2+4NaClO3=4NaCl+6H2O+6CO2
The chemical equation of tartaric acid and chlorate：
3C4H6O6+5NaClO3=5NaCl+9H2O+12CO2
From above-mentioned chemical equation, to decompose 1mol NaClO3On the basis of, it is respectively necessary for consuming 0.5mol lactic acid,
0.3mol citric acids, 3mol formic acid, 0.75mol oxalic acid or 0.6mol tartaric acid, i.e. need consumption 45g lactic acid, 57g citric acids,
138.09g formic acid, 67.53g oxalic acid or 90g tartaric acid.
As shown in the above, as decomposition 1molNaClO3When, the quality using lactic acid and citric acid is relatively minimal, because
This, in one embodiment, one kind that organic acid is selected in lactic acid and citric acid.
In one alternate embodiment, the mass fraction of organic acid is 5%-30%.
It should be noted that the mass fraction of organic acid is too low, then need addition very many when configuring organic acid soln
Water, and can dramatically increase the bearing capacity of the first cell body, reduce reaction efficiency, and if the mass fraction of organic acid is excessive,
Then organic acid is dispersed poor, can equally reduce reaction efficiency.
In one alternate embodiment, the pH of alkaline light salt brine is 10.Light salt brine after decomposition is adjusted to the pH value,
Most beneficial for follow-up salt dissolving process.
Embodiment 1
By the 0.5m in electrolytic cell3Light salt brine is drained to the first cell body, 4.5m3Light salt brine is drained to the second cell body, light salt brine
Water temperature be 85 DEG C, chloride hydrochlorate 10g/L (in terms of sodium chlorate) adds the breast that 57kg mass fractions are 20% in the first cell body
Acid is soluble in the compound of salt solution so that chlorate to be resolved into, and reacted solution is drained in the second cell body, in the second groove
The downstream of body sets dechlorinator, after dechlorinated tower processing, and solution ph is neutralized into 10 with the caustic soda of mass concentration 32%, and will
Solution after neutralization, which is delivered to, returns salt dissolving process progress refinement treatment after sulfate radical system, detection wherein chlorate content is
4.7g/L, qualified brine recirculation returns to electrolytic cell after processing.
Embodiment 2
By the 0.5m in electrolytic cell3Light salt brine is drained to the first cell body, 4.5m3Light salt brine is drained to the second cell body, light salt brine
Water temperature be 87 DEG C, chloride hydrochlorate 10g/L (in terms of sodium chlorate), it is 10% that 225kg mass fractions are added in the first cell body
Citric acid, chlorate is resolved into the compound for being soluble in salt solution, and reacted solution is drained in the second cell body,
The downstream of two cell bodies sets dechlorinator, and after dechlorinated tower processing, solution ph is neutralized into 11 with the caustic soda of mass concentration 30%,
And the solution after neutralization is delivered to returned after sulfate radical system salt dissolving process carry out refinement treatment, detection wherein chlorate contain
Measure as 2.55g/L, qualified brine recirculation return electrolytic cell after processing.
Embodiment 3
By the 0.5m in electrolytic cell3Light salt brine is drained to the first cell body, 4.5m3Light salt brine is drained to the second cell body, light salt brine
Water temperature be 86 DEG C, chloride hydrochlorate 10g/L (in terms of sodium chlorate), it is 15% that 345kg mass fractions are added in the first cell body
Formic acid, chlorate is resolved into the compound for being soluble in salt solution, reacted solution is drained in the second cell body, second
The downstream of cell body sets dechlorinator, after dechlorinated tower processing, and solution ph is neutralized into 11 with the caustic soda of mass concentration 30%, and
Solution after neutralization is delivered to salt dissolving process progress refinement treatment, detection wherein chlorate content are returned after sulfate radical system
For 2.1g/L, qualified brine recirculation returns to electrolytic cell after processing.
Embodiment 4
By the 0.5m in electrolytic cell3Light salt brine is drained to the first cell body, 4.5m3Light salt brine is drained to the second cell body, light salt brine
Water temperature be 88 DEG C, chloride hydrochlorate 10g/L (in terms of sodium chlorate), it is 18% that 130.4kg mass fractions are added in the first cell body
Oxalic acid, chlorate is resolved into the compound for being soluble in salt solution, reacted solution is drained in the second cell body,
The downstream of two cell bodies sets dechlorinator, and after dechlorinated tower processing, solution ph is neutralized into 11 with the caustic soda of mass concentration 30%,
And the solution after neutralization is delivered to returned after sulfate radical system salt dissolving process carry out refinement treatment, detection wherein chlorate contain
Measure as 2.63g/L, qualified brine recirculation return electrolytic cell after processing.
Embodiment 5
By the 0.5m in electrolytic cell3Light salt brine is drained to the first cell body, 4.5m3Light salt brine is drained to the second cell body, light salt brine
Water temperature be 86 DEG C, chloride hydrochlorate 10g/L (in terms of sodium chlorate), it is 26% that 127kg mass fractions are added in the first cell body
Tartaric acid, chlorate is resolved into the compound for being soluble in salt solution, and reacted solution is drained in the second cell body,
The downstream of two cell bodies sets dechlorinator, and after dechlorinated tower processing, solution ph is neutralized into 11 with the caustic soda of mass concentration 30%,
And the solution after neutralization is delivered to returned after sulfate radical system salt dissolving process carry out refinement treatment, detection wherein chlorate contain
Measure as 2.27g/L, qualified brine recirculation return electrolytic cell after processing.
Embodiment 6
0.5m3 light salt brines in electrolytic cell are drained to the first cell body, 4.5m3 light salt brines are drained to the second cell body, light salt
The water temperature of water is 85 DEG C, chloride hydrochlorate 10g/L (in terms of sodium chlorate), and it is 20% that 43kg mass fractions are added in the first cell body
Lactic acid and 45kg mass fractions are 25% citric acid, and chlorate is resolved into the compound for being soluble in salt solution, will be reacted
Solution is drained in the second cell body, dechlorinator is set in the downstream of the second cell body, after dechlorinated tower processing, with mass concentration 30%
Caustic soda solution ph is neutralized to 11, and the solution after neutralization delivered to the progress of salt dissolving process returned after sulfate radical system
Refinement treatment, detection wherein chlorate content is 1.82g/L, and qualified brine recirculation returns to electrolytic cell after processing.
Finally, the present processes are only preferably embodiment, are not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements made etc. should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. a kind of processing method of the chlorate in electrolytic cell light salt brine, it is characterised in that including：Add into electrolytic cell light salt brine
Enter organic acid.
2. processing method as claimed in claim 1, it is characterised in that further comprise：
A part of light salt brine in electrolytic cell is drained in the first cell body, organic acid is added into first cell body；
Another part light salt brine in electrolytic cell is drained in the second cell body, when the content of chlorate in first cell body is low
When 2g/L, the light salt brine in first cell body is drained in the second cell body.
3. processing method as claimed in claim 2, it is characterised in that the stream of light salt brine in first cell body and the second cell body
Amount is than being 1:10-15.
4. processing method as claimed in claim 3, it is characterised in that the stream of light salt brine in first cell body and the second cell body
Amount is than being 1:13.5.
5. the processing method as described in claim 1-4, it is characterised in that the organic acid include formic acid, oxalic acid, tartaric acid,
One or more in lactic acid and citric acid.
6. processing method as claimed in claim 5, it is characterised in that the organic acid is one kind in lactic acid and citric acid.
7. processing method as claimed in claim 6, it is characterised in that the mass fraction of the organic acid is 5%-30%.
8. processing method as claimed in claim 7, it is characterised in that also include：
The light salt brine that second cell body flows out is subjected to dechlorination processing, then caustic soda is added into the light salt brine handled by dechlorination
The light salt brine of alkalescence is carried out engaging sulphate processing by the pH to light salt brine in alkalescence.
9. processing method as claimed in claim 8, it is characterised in that the pH of the alkaline light salt brine is 10.
10. processing method as claimed in claim 9, it is characterised in that the temperature of the electrolytic cell light salt brine is 85-88 DEG C.
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| CN201710353738.XA CN107190278B (en) | 2017-05-18 | 2017-05-18 | A kind of processing method of chlorate in electrolytic cell light salt brine |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4405465A (en) * | 1982-06-30 | 1983-09-20 | Olin Corporation | Process for the removal of chlorate and hypochlorite from spent alkali metal chloride brines |
| CN102634813A (en) * | 2012-03-19 | 2012-08-15 | 山东东岳氟硅材料有限公司 | Method for increasing chlorate decomposition efficiency |
| US20130048509A1 (en) * | 2011-08-31 | 2013-02-28 | Shekar Balagopal | Electrochemical process to recycle aqueous alkali chemicals using ceramic ion conducting solid membranes |
| CN204022953U (en) * | 2014-08-11 | 2014-12-17 | 江苏理文化工有限公司 | A kind of production equipment of high purity sodium hydroxide |
-
2017
- 2017-05-18 CN CN201710353738.XA patent/CN107190278B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4405465A (en) * | 1982-06-30 | 1983-09-20 | Olin Corporation | Process for the removal of chlorate and hypochlorite from spent alkali metal chloride brines |
| US20130048509A1 (en) * | 2011-08-31 | 2013-02-28 | Shekar Balagopal | Electrochemical process to recycle aqueous alkali chemicals using ceramic ion conducting solid membranes |
| CN102634813A (en) * | 2012-03-19 | 2012-08-15 | 山东东岳氟硅材料有限公司 | Method for increasing chlorate decomposition efficiency |
| CN204022953U (en) * | 2014-08-11 | 2014-12-17 | 江苏理文化工有限公司 | A kind of production equipment of high purity sodium hydroxide |
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