CN102418114A - 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
- Publication number
- CN102418114A CN102418114A CN201110389283XA CN201110389283A CN102418114A CN 102418114 A CN102418114 A CN 102418114A CN 201110389283X A CN201110389283X A CN 201110389283XA CN 201110389283 A CN201110389283 A CN 201110389283A CN 102418114 A CN102418114 A CN 102418114A
- Authority
- CN
- China
- Prior art keywords
- salt solution
- salt
- ionic
- ionic membrane
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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 a kind of ionic membrane system alkali and use the brinish impurity-removing method, particularly ionic membrane system alkali is with micro Fe in the salt solution (CN)
6 4-Ionic removal method is particularly useful for all types of industries purified salt, powder salt as Fe (CN) in the salt brine solution of solute
6 4-Ionic is removed, and salt brine solution after treatment can be used for the production of ionic membrane system alkali.
Background technology
During ionic membrane system alkali is produced; The method that is employed in electrolytic brine in the ion-exchange membrane electrolyzer is produced caustic soda; The light salt brine that electrolysis produces through after the dechlorination again circulation get into the brinish preparation, the raw material salt solution for preparing through once, the secondary refining operation handles the back and gets into electrolyzer.Higher in the production process to the raw material brinish specification of quality that gets into electrolyzer, need carry out refinement treatment before going into groove, effectively reduce harmful ion content wherein.It is the gordian technique of ionic membrane basic industry that salt refining is handled, to ionic membrane life-span, bath voltage, current efficiency and quality product important influence.
At present the more employing purified salt of ionic membrane system alkali manufacturing enterprise is as raw material, because normal adding fluffy powder yellow prussiate (like yellow prussiate of potash) in the purified salt production process, makes and contains Fe (CN) in the raw material salt solution
6 4-Ion, this ion chemistry stable in properties, existing salt refining operation can't be removed, and with oxidized decomposition behind the salt solution entering electrolyzer, causes the interior Fe constituent content of electrolyzer to exceed standard Fe
2+Further be oxidized to 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, the ionic membrane lost of life.Fe (CN) in addition
6 4-The nitrogen element that ion is brought into makes electrolysis production exist and produces NCl
3Dangerous and Harmful Factors.
Better do not remove Fe (CN) during ionic membrane system alkali is produced at present
6 4-The ionic method generally adopts following approach to alleviate Fe (CN)
6 4-There is the influence that causes in ion: 1) yellow prussiate of potash content in the control 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-To the influence of ionic membrane, but effect is limited.The third mode still is in the research and development stage.Therefore develop and remove Fe (CN) in a kind of salt solution
6 4-Method, for prolonging ionic membrane work-ing life, ensureing that the normal operation of electrolysis process is significant.
Summary of the invention
The object of the invention is to overcome the defective of prior art, and a kind of Fe in oxygenant and the salt solution (CN) that utilizes is provided
6 4-Carry out oxidative decomposition, destroy Fe (CN)
6 4-Complex bonds, the Fe ionic ionic membrane system alkali of removing generation again after reaction finishes is with micro Fe in the salt solution (CN)
6 4-Ionic removal method.
Ionic membrane system alkali of the present invention is with micro Fe in the salt solution (CN)
6 4-Ionic removal method, the technical scheme that is adopted is following:
A. add oxygenant to ionic membrane system alkali in salt solution, carry out oxidative decomposition, the Fe in the salt solution (CN)
6 4-Complex bonds is destroyed, with Fe
2+Be oxidized to Fe
3+
B. after the oxidative decomposition of step a is accomplished, adopt existing salt refining operation to remove the Fe in the oxidation salt solution
3+, CN
-Ion finally is decomposed into N in the oxidative decomposition stage by complete oxidation
2And CO
2Or carbonate, remove micro Fe (CN) in the salt solution to reach
6 4-The ionic purpose.
Described oxygenant can be selected chlorine (Cl
2), hypochlorite, hypochlorous one or more.
Described oxygenant is that in the chlorine water that produces of chloride light salt brine, chloride anolyte, chlorine hydrogen operation that electrolyzer produces one or more are as oxygenant.Wherein the chloride light salt brine that produces of electrolyzer can be the forward and backward chloride light salt brine of vacuum dechlorination or air scavenging dechlorination one or both.
The oxygenant add-on does in the described oxidative decomposition, guarantees oxygenant and Fe (CN) in the reaction solution
6 4-Weight ratio greater than more than the 6:1.
Described oxidative decomposition temperature is at 60-100 ℃, and the reaction times is 5-90min, and the pH value is 6-10.
Described oxidative decomposition is executed at and contains Fe (CN)
6 4After the raw material salinization water dissolution, before the salt refining.
Described oxidative decomposition finishes the removing method of back Fe element, main utilize existing salt solution once, the secondary refining operation removes.
Fe in the described salt solution (CN)
6 4-Ion is by containing Fe (CN)
6 4-Bring into after the ionic raw material salinization water dissolution, raw material salt can comprise one or more in all kinds of purified salts and the powder salt.
Described oxidizing reaction finishes the Fe (CN) in the salt solution of back
6 4-Content is by reducing to more than the 0.20mg/l below the 0.01mg/l, and total cyanide content is lower than 0.05mg/l, handles the total Fe in back through the salt refining operation and is lower than 20ug/L, satisfies the production requirement of ionic membrane system alkali fully.
The ionic membrane system of the present invention is directed to alkali is with the micro Fe that is contained in the salt solution (CN)
6 4-, adopt the adding oxygenant to carry out oxidative decomposition, Fe (CN)
6 4-Complex bonds is destroyed, wherein Fe
2+Be oxidized to Fe
3+, finish the back in oxidative decomposition and utilize existing salt refining operation to remove Fe element, CN
-Ion finally is decomposed into carbonate or N in the oxidative decomposition stage by complete oxidation
2And CO
2Or carbonate, remove micro Fe (CN) in the salt solution to reach
6 4-The ionic purpose.Technology 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 the salt solution of back
6 4-Content is by reducing to more than the 0.20mg/l below the 0.01mg/l, and total cyanide content is lower than 0.05mg/l, handles the total Fe in back through the salt refining operation and is lower than 0.1mg/L, satisfies the production requirement of ionic membrane system alkali fully.
Embodiment
Through following instance to invention to further describing, but protection scope of the present invention is not limited thereto.
Embodiment 1
The aqueous sodium hypochlorite solution adding is contained Fe (CN)
6 4-Salt brine solution carry out oxidative decomposition, the initial Fe of reaction solution (CN)
6 4-Concentration is 0.2mg/l, and Youxiaolin concentration is 1.2mg/l, keeps 100 ℃ of temperature of reaction, reaction times 90min, and the pH value is 8, reaction finishes back Fe (CN)
6 4-Content is less than 0.01mg/l, total cyanide content 0.055mg/l, reaction back salt solution through chemical dechlorination, salt solution once, to handle the total Fe content in back be 0.1mg/l to the secondary refining operation.
Embodiment 2
To come out from electrolyzer, adding contains Fe (CN) through the light salt brine after the vacuum dechlorination
6 4-Salt brine solution carry out oxidative decomposition, the initial Fe of reaction solution (CN)
6 4-Concentration is 0.4mg/l, and free chloro concentration is 40mg/l, keeps 80 ℃ of temperature of reaction, reaction times 60min, and the pH value is that 7 reactions finish back Fe (CN)
6 4-Content is less than 0.01mg/l, and total cyanogen (CN) content is lower than 0.015mg/l, reaction back salt solution again through chemical dechlorination, salt solution once, to handle the total Fe content in back be 0.06mg/l to the secondary refining operation.
Embodiment 3
The chlorine feeding is contained Fe (CN)
6 4-Salt brine solution mix and to carry out oxidative decomposition, the initial Fe of reaction solution (CN)
6 4-Concentration is 2mg/l, and free chloro concentration is 120mg/l, keeps 70 ℃ of temperature of reaction, reaction times 30min, and the pH value is 10, reaction finishes back Fe (CN)
6 4-Content is less than 0.01mg/l, and total cyanogen (CN) content is lower than 0.001mg/l, reaction back salt solution again through chemical dechlorination, salt solution once, to handle the total Fe content in back be 0.03mg/l to the secondary refining operation.
Embodiment 4
The chlorine water that the light salt brine that will come out from electrolyzer, chlorine hydrogen treatment process produce adds in proportion and contains Fe (CN)
6 4-Salt brine solution carry out oxidative decomposition, the initial Fe of reaction solution (CN)
6 4-Concentration is 3mg/l, and free chloro concentration is 1300mg/l, keeps 50 ℃ of temperature of reaction, reaction times 5min, and the pH value is 6, reaction finishes back Fe (CN)
6 4-Content is less than 0.01mg/l, and total cyanogen (CN) content is lower than 0.001mg/l, reaction back salt solution again through vacuum dechlorination, chemical dechlorination, salt solution once, to handle the total Fe content in back be 0.009mg/l to the secondary refining operation.
Claims (9)
1. an ionic membrane system alkali is with micro Fe in the salt solution (CN)
6 4-Ionic removal method is characterized in that, its method is:
A. add oxygenant to ionic membrane system alkali in salt solution, carry out oxidative decomposition, the Fe in the salt solution (CN)
6 4-Complex bonds is destroyed, with Fe
2+Be oxidized to Fe
3+
B. after the oxidative decomposition of step a is accomplished, adopt existing salt refining operation to remove the Fe in the oxidation salt solution
3+, CN
-Ion finally is decomposed into N in the oxidative decomposition stage by complete oxidation
2And CO
2Or carbonate, to remove micro Fe (CN) in the salt solution
6 4-Ion.
2. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1
6 4-Ionic removal method is characterized in that, described oxygenant can be selected chlorine (Cl
2), hypochlorite, hypochlorous one or more.
3. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1 and 2
6 4-Ionic removal method; It is characterized in that; Described oxygenant be in the chlorine water that produces of chloride light salt brine, chloride anolyte, chlorine hydrogen operation that electrolyzer produces one or more as oxygenant, wherein the chloride light salt brine that produces of electrolyzer be the forward and backward chloride light salt brine of vacuum dechlorination or air scavenging dechlorination one or both.
4. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1 to 3
6 4-Ionic removal method is characterized in that, the oxygenant add-on does in the described oxidative decomposition, guarantees oxygenant and Fe (CN) in the reaction solution
6 4-Weight ratio greater than more than the 6:1.
5. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1
6 4Ion
-The removal method, it is characterized in that described oxidative decomposition temperature is at 60-100 ℃, the reaction times is 5-90min, the pH value is 6-10.
6. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1
6 4-The removal method, it is characterized in that described oxidative decomposition is executed at and contains Fe (CN)
6 4After the raw material salinization water dissolution, before the salt refining.
7. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1
6 4-Ionic removal method is characterized in that, described oxidative decomposition finishes the removing method of back Fe element, main utilize existing salt solution once, the secondary refining operation removes.
8. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1 and 6
6 4Ion
-The removal method, it is characterized in that the Fe in the described salt solution (CN)
6 4-Ion is by containing Fe (CN)
6 4-Bring into after the ionic raw material salinization water dissolution, raw material salt can comprise one or more in all kinds of purified salts and the powder salt.
9. require described a kind of ionic membrane system alkali with micro Fe in the salt solution (CN) like right 1
6 4-Ionic removal method is characterized in that, oxidizing reaction finishes the Fe (CN) in the salt solution of back
6 4-Content is by reducing to more than the 0.20mg/l below the 0.01mg/l, and total cyanide content is lower than 0.05mg/l, handles the total Fe in back through the salt refining operation and 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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102418114A true CN102418114A (en) | 2012-04-18 |
| CN102418114B CN102418114B (en) | 2014-05-07 |
Family
ID=45942753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110389283.XA Expired - Fee Related 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102418114B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201531A (en) * | 2017-04-27 | 2017-09-26 | 新疆中泰化学阜康能源有限公司 | Highly acid light salt brine reclamation set after chlorate decomposer is decomposed 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 |
-
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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201531A (en) * | 2017-04-27 | 2017-09-26 | 新疆中泰化学阜康能源有限公司 | Highly acid light salt brine reclamation set after chlorate decomposer is decomposed in electrolysis process |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102418114B (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6223442B2 (en) | Method and apparatus for producing or recovering hydrochloric acid from a metal salt solution | |
| NO20075881L (en) | Method of treating a spent sulfur-containing caustic refinery stream using a membrane electrolyzer powered by a fuel cell | |
| CN105621764A (en) | Treatment process of epoxy chloropropane production wastewater | |
| KR101269948B1 (en) | Apparatus and method for nitrogen wastewater treatment | |
| RU2509829C2 (en) | Method of producing chlorine, caustic soda and hydrogen | |
| WO2013176111A1 (en) | Processing method and apparatus for copper chloride-containing acidic waste liquids | |
| JP5745426B2 (en) | Removal of perchlorate from concentrated salt solutions using amphoteric ion exchange resins | |
| CN111087047A (en) | Treatment method of bromine-containing organic wastewater | |
| KR101910635B1 (en) | Method for treating wastewater from flue gas desulfurization using electrolysis device | |
| CN102418114B (en) | Method for removing trace quantity of Fe(CN)6<4->ions in saline for ionic membrane alkali manufacturing | |
| JPH07100466A (en) | Method for treating waste water | |
| CN105293526A (en) | Method for purifying iodine in saline water of ionic membrane caustic soda production process | |
| KR101638971B1 (en) | Wet gas cleaning system using oxidizing agent produced from the wastewater | |
| EP1480913B1 (en) | Nitrate removal | |
| CN114293207A (en) | System and method for decomposing chlorate in caustic soda production by ion-exchange membrane method | |
| CN105084602A (en) | Method for degrading COD in strong brine | |
| JPH07237919A (en) | Method for purification of alkali metal chloride water solution and its plant | |
| US20180119298A1 (en) | Iodide removal from brine using ion retardation resins | |
| JP5913087B2 (en) | Wastewater treatment system | |
| JPH06182344A (en) | Decomposition and utilization method and device for salt and inorganic nitrogen compound-containing solution | |
| JP3568294B2 (en) | How to prevent chlorate from increasing in salt water | |
| CN109811366A (en) | A method of decomposing chlorate in electrolysis cycle light salt brine | |
| JP4436183B2 (en) | Iodine ion removal process and electrolysis process | |
| JP7494216B2 (en) | PFAS Treatment Scheme Using Separation and Electrochemical Rejection | |
| JP2001113290A (en) | Apparatus for treating organic matter-containing water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140507 Termination date: 20171130 |