CN102418114B - Method for removing trace quantity of Fe(CN)6<4->ions in saline for ionic membrane alkali manufacturing - Google Patents
Method for removing trace quantity of Fe(CN)6<4->ions in saline for ionic membrane alkali manufacturing Download PDFInfo
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- CN102418114B CN102418114B CN201110389283.XA CN201110389283A CN102418114B CN 102418114 B CN102418114 B CN 102418114B CN 201110389283 A CN201110389283 A CN 201110389283A CN 102418114 B CN102418114 B CN 102418114B
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Abstract
The invention discloses a method for removing trace quantity of Fe(CN)6<4->ions in saline for ionic membrane alkali manufacturing, and relates to a method for removing impurities in saline for ionic membrane alkali manufacturing, in particular to a method for removing trace quantity of Fe(CN)6<4->ions in saline for ionic membrane alkali manufacturing. The method comprises the following steps of: a, adding an oxidant into the saline for the ionic membrane alkali manufacturing, performing oxygenolysis reaction, breaking a Fe(CN)6<4-> complexing bond in the saline, and oxidizing Fe<2+> to form Fe<3+>; and b, after the oxygenolysis reaction is finished, removing Fe<3+> from the oxidized saline by the conventional saline refining process, wherein CN<-> ions are oxidized completely in the oxygenolysis reaction stage and are decomposed into N2 and CO2 or carbonate finally and thus, a trace amount of Fe(CN)6<4->ions in the saline are removed. The method has a simple process and is mild in reaction condition and low in operating cost, and new pollutants are avoided.
Description
Technical field
The present invention relates to the impurity-removing method of salt solution for a kind of ionic membrane alkaline, particularly micro Fe (CN) in salt solution for ionic membrane alkaline
6 4-the removal method of ion, is particularly useful for all types of industries purified salt, powder salt as Fe(CN in the salt brine solution of solute)
6 4-the removal of ion, salt brine solution after treatment can be used for ionic membrane alkaline and produces.
Background technology
During ionic membrane alkaline is produced, the method of employing electrolytic brine in ion-exchange membrane electrolyzer is produced caustic soda, the light salt brine that electrolysis the produces preparation that circulation enters salt solution again after dechlorination, the raw material salt solution preparing through once, secondary refining operation enters electrolyzer after processing.Higher to entering the specification of quality of raw material salt solution of electrolyzer in production process, need to carry out refinement treatment before entering groove, effectively reduce harmful ion content wherein.It is the gordian technique of ionic membrane basic industry that salt refining is processed, and service life of ion-exchange membrane, bath voltage, current efficiency and quality product are had to important impact.
The more employing purified salt of ionic membrane alkaline manufacturing enterprise, as raw material, owing to often adding fluffy powder yellow prussiate (as yellow prussiate of potash) in purified salt production process, makes to contain Fe(CN in raw material salt solution at present)
6 4-ion, this ion chemistry stable in properties, existing salt refining operation cannot be removed, and with salt solution, enters oxidized decomposition after electrolyzer, causes Fe constituent content in electrolyzer to exceed standard, Fe
2+be further oxided as Fe
3+, with OH
-form Fe(OH)
3, be deposited on ionic membrane surface and anolyte flexible pipe, cause that voltage rises, current efficiency reduces, flexible pipe reddens, service life of ion-exchange membrane shortens.Fe(CN in addition)
6 4-the nitrogen element that ion is brought into exists electrolysis production and produces NCl
3dangerous and Harmful Factors.
Ionic membrane alkaline is not better removed Fe(CN in producing at present)
6 4-the method of ion, generally adopts following approach to alleviate Fe(CN)
6 4-there is the impact causing in ion: 1) controls yellow prussiate of potash content in raw material salt; 2) control anolyte acidity; 3) use novel fluffy powder, substitute yellow prussiate of potash.First and second mode can alleviate Fe(CN)
6 4-impact on ionic membrane, but effect is limited.The third mode is still in the research and development stage.Therefore develop in a kind of salt solution and remove Fe(CN)
6 4-method, for extend ionic exchange membrane serve-time, ensure that the normal operation of electrolysis process is significant.
Summary of the invention
The object of the invention is to overcome the defect of prior art, and a kind of Fe(CN in oxygenant and salt solution that utilizes is provided)
6 4-carry out oxidative decomposition, destroy Fe(CN)
6 4-complex bonds, the micro Fe (CN) in salt solution for ionic membrane alkaline of the Fe ion that after reaction finishes, removal produces again
6 4-the removal method of ion.
Micro Fe (CN) in salt solution for ionic membrane alkaline of the present invention
6 4-the removal method of ion, the technical scheme adopting is as follows:
A. to ionic membrane alkaline with adding oxygenant in salt solution, carry out oxidative decomposition, by the Fe(CN in salt solution)
6 4-complex bonds is destroyed, by Fe
2+be oxidized to Fe
3+;
B., after the oxidative decomposition of step a completes, adopt existing salt refining operation to remove the Fe in oxidation salt solution
3+, CN
-ion is finally decomposed into N in the oxidative decomposition stage by complete oxidation
2and CO
2or carbonate, to reach, remove micro Fe (CN) in salt solution
6 4-the object of ion.
Described oxygenant can be selected chlorine (Cl
2), hypochlorite, hypochlorous one or more.
Described oxygenant is that one or more in the chlorine water that produces of chloride light salt brine, chloride anolyte, chlorine hydrogen operation that electrolyzer produces are as oxygenant.The chloride light salt brine that wherein electrolyzer produces can be vacuum dechlorination or the forward and backward chloride light salt brine of air scavenging dechlorination one or both.
In described oxidative decomposition, oxygenant add-on is, guarantees oxygenant and Fe(CN in reaction solution)
6 4-weight ratio be greater than 6:1 more than.
Described oxidative decomposition temperature is at 60-100 ℃, and the reaction times is 5-90min, and pH value is 6-10.
Described oxidative decomposition is executed at containing Fe(CN)
6 4after raw material salinization water dissolution, before salt refining.
Described oxidative decomposition finishes the removing method of rear Fe element, mainly utilize existing salt solution once, secondary refining operation removes.
Fe(CN in described salt solution)
6 4-ion is by containing Fe(CN)
6 4-after the raw material salinization water dissolution of ion, bring into, raw material salt can comprise one or more in all kinds of purified salts and powder salt.
Described oxidizing reaction finishes the Fe(CN in rear salt solution)
6 4-content is down to below 0.01mg/l above by 0.20mg/l, and total cyanide content is lower than 0.05mg/l, and after salt refining operation is processed, total Fe, lower than 20ug/L, meets the production requirement of ionic membrane alkaline completely.
The present invention is directed to contained micro Fe (CN) in salt solution for ionic membrane alkaline
6 4-, adopt and add oxygenant to carry out oxidative decomposition, Fe(CN)
6 4-complex bonds is destroyed, wherein Fe
2+be oxidized to Fe
3+, after oxidative decomposition finishes, utilize existing salt refining operation to remove Fe element, CN
-ion is finally decomposed into carbonate or N in the oxidative decomposition stage by complete oxidation
2and CO
2or carbonate, to reach, remove micro Fe (CN) in salt solution
6 4-the object of ion.Technique of the present invention is simple, and reaction conditions is gentle, and running cost is low, does not produce new pollution substance, and oxidizing reaction finishes the Fe(CN in rear salt solution)
6 4-content is down to below 0.01mg/l above by 0.20mg/l, and total cyanide content is lower than 0.05mg/l, and after salt refining operation is processed, total Fe, lower than 0.1mg/L, meets the production requirement of ionic membrane alkaline completely.
Embodiment
By following instance to invention to further describing, but protection scope of the present invention is not limited to this.
Embodiment 1
Aqueous sodium hypochlorite solution is added containing Fe(CN)
6 4-salt brine solution carry out oxidative decomposition, the initial Fe(CN of reaction solution)
6 4-concentration is 0.2mg/l, and clorox concentration is 1.2mg/l, maintains 100 ℃ of temperature of reaction, reaction times 90min, and pH value is 8, reaction finishes rear Fe(CN)
6 4-content is less than 0.01mg/l, total cyanide content 0.055mg/l, after reaction salt solution through chemical dechlorination, salt solution once, secondary refining operation after processing total Fe content be 0.1mg/l.
Embodiment 2
By from electrolyzer out the light salt brine after vacuum dechlorination add containing Fe(CN)
6 4-salt brine solution carry out oxidative decomposition, the initial Fe(CN of reaction solution)
6 4-concentration is 0.4mg/l, and free chloro concentration is 40mg/l, maintains 80 ℃ of temperature of reaction, reaction times 60min, pH value is that 7 reactions finish rear Fe(CN)
6 4-content is less than 0.01mg/l, and total cyanogen (CN) content is lower than 0.015mg/l, after reaction salt solution again through chemical dechlorination, salt solution once, secondary refining operation after processing total Fe content be 0.06mg/l.
Embodiment 3
Chlorine is passed into containing Fe(CN)
6 4-salt brine solution mix carry out oxidative decomposition, the initial Fe(CN of reaction solution)
6 4-concentration is 2mg/l, and free chloro concentration is 120mg/l, maintains 70 ℃ of temperature of reaction, reaction times 30min, and pH value is 10, reaction finishes rear Fe(CN)
6 4-content is less than 0.01mg/l, and total cyanogen (CN) content is lower than 0.001mg/l, after reaction salt solution again through chemical dechlorination, salt solution once, secondary refining operation after processing total Fe content be 0.03mg/l.
Embodiment 4
The chlorine water producing from light salt brine out of electrolyzer, chlorine hydrogen treatment process is added in proportion containing Fe(CN)
6 4-salt brine solution carry out oxidative decomposition, the initial Fe(CN of reaction solution)
6 4-concentration is 3mg/l, and free chloro concentration is 1300mg/l, maintains 50 ℃ of temperature of reaction, reaction times 5min, and pH value is 6, reaction finishes rear Fe(CN)
6 4-content is less than 0.01mg/l, and total cyanogen (CN) content is lower than 0.001mg/l, after reaction salt solution again through vacuum dechlorination, chemical dechlorination, salt solution once, secondary refining operation after processing total Fe content be 0.009mg/l.
Claims (2)
1. micro Fe (CN) in salt solution for an ionic membrane alkaline
6 4-the removal method of ion, is characterized in that, its method is:
A. to ionic membrane alkaline with adding oxygenant in salt solution, carry out oxidative decomposition, by the Fe(CN in salt solution)
6 4-complex bonds is destroyed, by Fe
2+be oxidized to Fe
3+;
B., after the oxidative decomposition of step a completes, adopt existing salt refining operation to remove the Fe in oxidation salt solution
3+, CN
-ion is finally decomposed into N in the oxidative decomposition stage by complete oxidation
2and CO
2or carbonate, to remove micro Fe in salt solution (CN)
6 4-ion, described oxygenant be chlorine, hypochlorite, hypochlorous one or more, or described oxygenant be one or more in the chlorine water that produces of chloride light salt brine, chloride anolyte, chlorine hydrogen operation that electrolyzer produces as oxygenant, the chloride light salt brine that wherein electrolyzer produces be the forward and backward chloride light salt brine of vacuum dechlorination or air scavenging dechlorination one or both.
2. micro Fe (CN) in salt solution for a kind of ionic membrane alkaline as claimed in claim 1
6 4-the removal method of ion,
It is characterized in that, in described oxidative decomposition, oxygenant add-on is, guarantees oxygenant and Fe(CN in reaction solution)
6 4-weight ratio be greater than 6:1 more than.
3. micro Fe (CN) in salt solution for a kind of ionic membrane alkaline as claimed in claim 1
6 4-the removal method of ion,
It is characterized in that, described oxidative decomposition temperature is at 60-100 ℃, and the reaction times is 5-90min, and pH value is 6-10.
4. micro Fe (CN) in salt solution for a kind of ionic membrane alkaline as claimed in claim 1
6 4-the removal method of ion, is characterized in that, described oxidative decomposition is executed at containing Fe(CN)
6 4-after raw material salinization water dissolution, before salt refining.
5. micro Fe (CN) in salt solution for a kind of ionic membrane alkaline as claimed in claim 1
6 4-the removal method of ion, is characterized in that, described oxidative decomposition finishes the removing method of rear Fe element, mainly utilize existing salt solution once, secondary refining operation removes.
6. micro Fe (CN) in salt solution for a kind of ionic membrane alkaline as described in claim 1 or 4
6 4-the removal method of ion, is characterized in that, the Fe(CN in described salt solution)
6 4-ion is by containing Fe(CN)
6 4-after the raw material salinization water dissolution of ion, bring into, raw material salt comprises one or more in all kinds of purified salts and powder salt.
7. micro Fe (CN) in salt solution for a kind of ionic membrane alkaline as claimed in claim 1
6 4-the removal method of ion, is characterized in that, oxidizing reaction finishes the Fe(CN in rear salt solution)
6 4-content is down to below 0.01mg/L above by 0.20mg/L, and total cyanide content is lower than 0.05mg/L, and after salt refining operation is processed, total Fe is lower than 0.1mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110389283.XA CN102418114B (en) | 2011-11-30 | 2011-11-30 | Method for removing trace quantity of Fe(CN)6<4->ions in saline for ionic membrane alkali manufacturing |
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|---|---|---|---|
| CN201110389283.XA CN102418114B (en) | 2011-11-30 | 2011-11-30 | Method for removing trace quantity of Fe(CN)6<4->ions in saline for ionic membrane alkali manufacturing |
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|---|---|
| CN102418114A CN102418114A (en) | 2012-04-18 |
| CN102418114B true CN102418114B (en) | 2014-05-07 |
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|---|---|---|---|---|
| CN107201531B (en) * | 2017-04-27 | 2020-10-30 | 新疆中泰化学阜康能源有限公司 | Strong acid light salt water recycling device after chlorate decomposer decomposes in electrolysis process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2714539Y (en) * | 2004-07-08 | 2005-08-03 | 山东滨化集团有限责任公司 | Primary salt water purifying device for production of ion film caustic soda |
| CN102120590A (en) * | 2011-01-25 | 2011-07-13 | 乳源东阳光电化厂 | Method and system for refining crude brine |
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2011
- 2011-11-30 CN CN201110389283.XA patent/CN102418114B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2714539Y (en) * | 2004-07-08 | 2005-08-03 | 山东滨化集团有限责任公司 | Primary salt water purifying device for production of ion film caustic soda |
| CN102120590A (en) * | 2011-01-25 | 2011-07-13 | 乳源东阳光电化厂 | Method and system for refining crude brine |
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|---|---|
| CN102418114A (en) | 2012-04-18 |
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