CN101293661B - Ionic membrane caustic soda light salt brine fine purification technique - Google Patents
Ionic membrane caustic soda light salt brine fine purification technique Download PDFInfo
- Publication number
- CN101293661B CN101293661B CN2008100499974A CN200810049997A CN101293661B CN 101293661 B CN101293661 B CN 101293661B CN 2008100499974 A CN2008100499974 A CN 2008100499974A CN 200810049997 A CN200810049997 A CN 200810049997A CN 101293661 B CN101293661 B CN 101293661B
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- CN
- China
- Prior art keywords
- brine
- salt
- dechlorination
- add
- sent
- 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.)
- Expired - Fee Related
Links
- 239000012267 brine Substances 0.000 title claims abstract description 56
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 56
- 150000003839 salts Chemical class 0.000 title claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 title claims abstract description 36
- 235000011121 sodium hydroxide Nutrition 0.000 title claims abstract description 12
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 239000012528 membrane Substances 0.000 title claims description 8
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 159000000009 barium salts Chemical class 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 16
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007670 refining Methods 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract 2
- 235000010265 sodium sulphite Nutrition 0.000 abstract 2
- 230000007423 decrease Effects 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 235000017168 chlorine Nutrition 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 9
- 241000195493 Cryptophyta Species 0.000 description 4
- 241000233866 Fungi Species 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229940045511 barium chloride Drugs 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a refining process for fresh brine of ion film caustic soda, in particular to dechlorination of the fresh brine and desorption of organics in the fresh brine; wherein, the fresh brine from an ion-exchange membrane electrolyzer is dechlorinated by a dechlorination tower to a range that the process allows, sent to a first brine process, added barium salt to remove sulfate radical brought in the system by material salt, and then is sent to a salt dissolving tank after water distribution; crude brine from the salt dissolving tank is added a refining agent for purification, Na2SO3 for dechlorination and a PH regulator in sequence, and then is sent to a second brine process after processing. The process is simple, reduces the process of adding Na2SO3 in a dechlorinationsystem and that of adding NaClO in a brine refining system, reduces the variety and quantity of additives, decreases equipment investment and correspondingly saves power consumption of the part as well as alleviates the environmental pollution.
Description
(1) technical field
The present invention relates to ionic membrane caustic soda light salt brine fine purification technique, particularly light salt brine dechlorination and wherein organic removing.
(2) background technology
In ion film caustic soda is produced, the light salt brine that comes out from ion-exchange membrane electrolyzer will being used to of returning salt system salt, but owing to contain a large amount of free chlorines in the light salt brine, for alleviating it to equipments in brine system and Corrosion of Pipeline, will pass through dechlorinator's dechlorination, but the free chlorine that still contains the 10-100mg/L that has an appointment after the dechlorination is (mainly with ClO
-Form exists), add reducing substances Na then
2SO
3And ClO
-Free chlorine is thoroughly removed in reaction.
ClO
-+SO
3 2-→SO
4 2-+Cl
-
Deliver to the primary brine operation through the later light salt brine of thorough dechlorination, add BaCl
2Remove by crude salt and add Na
2SO
3Bring the sulfate radical of system into, salt dissolving tank salt is sent in water distribution then; From the crude brine that salt dissolving tank comes out, need to add NaClO and remove organism and fungus algae, add finishing agent then and remove Ca
2+, Mg
2+Deng impurity, add Na again
2SO
3And the PH conditioning agent, remove unnecessary ClO
-After send to secondary brine.Its process flow diagram is seen Fig. 1.This scheme finally can be removed the free chlorine in the light salt brine and the organism of existence, but also has the following disadvantages:
1, need in the dechlorination system, add reducing substances Na
2SO
3Both caused Na
2SO
3Waste, need to increase Na again
2SO
3Dosing apparatus and pipeline, complex technical process.
2, the Na of Jia Ruing
2SO
3Cause brine system SO
4 2-Foreign matter content increases, SO
4 2-Existence not only can influence work-ing life of electrolytic efficiency and film, also need to add again BaCl
2Remove, increased production cost, also increased the salt mud emission amount.
3, need to add NaClO in the salt refining process and remove organism and fungus algae impurity, both caused the NaClO waste, need to increase NaClO dosing apparatus and pipeline, complex technical process again.
(3) summary of the invention
The object of the present invention is to provide a kind of ionic membrane caustic soda light salt brine fine purification technique, can remove chlorine in the light salt brine and organism, can simplify technology again, reduce the kind and the consumption of additive, cost and facility investment economize in raw materials.
The technical solution used in the present invention is as follows:
Ionic membrane caustic soda light salt brine fine purification technique, the light salt brine that will come out from ion-exchange membrane electrolyzer to the technology allowed band, is delivered to the primary brine operation through dechlorinator's dechlorination then, add barium salt remove bring the sulfate radical of system into by raw material salt after, salt dissolving tank is sent in water distribution; From the crude brine that salt dissolving tank comes out, add the finishing agent removal of impurities successively, add Na
2SO
3Remove free chlorine and PH conditioning agent, send to secondary brine after the processing.
This technology utilization light salt brine after dechlorinator's dechlorination in the salt solution still residual free chlorine (principal mode is ClO
-) needing in original technology to replace the NaClO that adds to remove organism and fungus algae impurity in the primary brine, this adds Na before just having been avoided entering the primary brine operation
2SO
3Come dechlorination, and the primary brine operation need add NaClO and removes organism; In the corresponding primary brine operation, only need to add and remove the required barium salt of sulfate radical that raw material salt brings system into and get final product, because of removing aforementioned Na
2SO
3The barium salt of the sulfate radical that increases of adding then need not to add; And at last before entering the secondary brine operation, because the free chlorine major part in the salt solution consumes the Na of adding in the organism subtractive process
2SO
3Amount also less; And, just reduced the investment of equipment accordingly because of the minimizing of additive types.Though because free chlorine also was present in before removing organism in the light salt brine, can form certain corrosion to the equipment pipe of process in this process, the amount of residual free chlorine is fewer, therefore in the long run, this technology still has great advantage.
The removal of impurities of above-described adding finishing agent mainly is meant removes Ca
2+, Mg
2+Deng impurity, the kind of finishing agent and quantity are according to the difference of foreign matter content in the technology difference that adopts, the salt solution, and those skilled in the art can adjust.
The light salt brine that comes out as for ion-exchange membrane electrolyzer after dechlorinator's dechlorination the control of the free chlorine in the solution what proper can be according to crude brine in organism remove required amount and adjust, make it both to satisfy every index request that electrolysis with ion-exchange film is produced, satisfy the requirement of organic matter removal and fungus algae in the primary brine refining system again, and guaranteeing that production system is stable, this all is that those skilled in the art can calculate adjustment.The free chlorine that returns in the light salt brine behind the feasible process of the control adjustment dechlorinator in this technology is 5-50mg/L.
The present invention has following advantage with respect to prior art:
Technology of the present invention is simple, has reduced the dechlorination system and has added Na
2SO
3Operation and salt refining system add the NaClO operation; Reduced the kind and the consumption of additive: the dechlorination system need not add Na
2SO
3, the salt refining system need not add NaClO, has reduced BaCl
2And Na
2SO
3Addition; Reduced facility investment: saved Na
2SO
3With NaClO preparation and adding set, also saved the power consumption of this part accordingly; Pollute and reduce: the SO that produces in the system
4 2-Content reduces, and therefore removes SO
4 2-The outer discharge capacity of glaur also reduced, alleviated pollution to environment.
(4) description of drawings
Fig. 1 is the FB(flow block) of traditional brine rectification process;
Fig. 2 is the FB(flow block) of brine rectification process in the embodiment of the invention 1.
(5) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
Ionic membrane caustic soda light salt brine fine purification technique, to regulate pH from the light salt brine that ion-exchange membrane electrolyzer comes out is 2.0, pump into the dechlorination of vacuum dechlorination tower then, the free chlorine content that detects in the salt solution after the dechlorination is 40mg/L, deliver to the primary brine operation then, add bariumchloride remove bring the sulfate radical of system into by raw material salt after, salt dissolving tank is sent in water distribution; From the crude brine that salt dissolving tank comes out, add NaOH, FeCl successively
3Finishing agent is removed magnesium ion, and then adds Na
2CO
3Finishing agent is removed calcium ion, and re-adjustment pH value is 10 behind membrane filtration, every liter of Na that adds 25mg
2SO
3Dechlorination, free chlorine is lower than detection limit in the salt solution after handling after testing, and organic content reaches below the 10mg/L, sends to secondary brine then.
Embodiment 2
Ionic membrane caustic soda light salt brine fine purification technique, to regulate pH to 1.3 from the light salt brine that ion-exchange membrane electrolyzer comes out, pump into the dechlorination of vacuum dechlorination tower then, the free chlorine content that detects in the salt solution after the dechlorination is 15mg/L, deliver to the primary brine operation then, add bariumchloride remove bring the sulfate radical of system into by raw material salt after, salt dissolving tank is sent in water distribution; From the crude brine that salt dissolving tank comes out, add NaOH, FeCl successively
3Finishing agent is removed magnesium ion, and then adds Na
2CO
3Finishing agent is removed calcium ion, and re-adjustment pH value is 9 behind membrane filtration, every liter of Na that adds 2mg
2SO
3Dechlorination, free cl content is lower than detection limit in the salt solution after handling after testing, and organic content reaches below the 10mg/L, sends to secondary brine then.
Claims (1)
1. ionic membrane caustic soda light salt brine fine purification technique, it is characterized in that the light salt brine that will come out from ion-exchange membrane electrolyzer is 5-50mg/L through dechlorinator's dechlorination to the free chlorine the salt solution, deliver to the primary brine operation then, add barium salt remove bring the sulfate radical of system into by raw material salt after, salt dissolving tank is sent in water distribution; From the crude brine that salt dissolving tank comes out, add the finishing agent removal of impurities successively, add Na
2SO
3Secondary brine is sent in dechlorination and pH regulator agent after the processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100499974A CN101293661B (en) | 2008-06-11 | 2008-06-11 | Ionic membrane caustic soda light salt brine fine purification technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100499974A CN101293661B (en) | 2008-06-11 | 2008-06-11 | Ionic membrane caustic soda light salt brine fine purification technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101293661A CN101293661A (en) | 2008-10-29 |
| CN101293661B true CN101293661B (en) | 2010-08-04 |
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ID=40064253
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100499974A Expired - Fee Related CN101293661B (en) | 2008-06-11 | 2008-06-11 | Ionic membrane caustic soda light salt brine fine purification technique |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259961B (en) * | 2011-05-18 | 2013-04-17 | 建滔（衡阳）实业有限公司 | Method for comprehensively utilizing supernatant of calcium carbide slurry and dilute brine generated by electrolysis |
| CN103382033B (en) * | 2013-06-26 | 2016-05-11 | 山东大地盐化集团有限公司 | A kind of substep extracts the technique of the solid matter of salt refining process generation |
| CN103601272B (en) * | 2013-11-22 | 2015-08-26 | 新汶矿业集团有限责任公司泰山盐化工分公司 | Adopt the method for dechlorination light salt brine preparation finishing agent |
| CN104030485B (en) * | 2014-05-29 | 2016-04-13 | 新疆中泰化学股份有限公司 | Electrolysis crude brine removal of impurities treatment unit and treatment process thereof |
| CN104532283B (en) * | 2014-12-17 | 2016-01-13 | 济宁金威煤电有限公司 | A kind of light salt brine replaces method and the device of part refined brine electrolysis caustic soda |
| CN104860335A (en) * | 2015-05-07 | 2015-08-26 | 芜湖融汇化工有限公司 | Refining method for removing chlorate from salt water |
| CN113463132A (en) * | 2021-06-30 | 2021-10-01 | 华融化学股份有限公司 | Ammonium removal system and ammonium removal method for chlor-alkali industry |
| CN113753918B (en) * | 2021-09-24 | 2023-02-03 | 攀枝花钢企欣宇化工有限公司 | Method for reusing vanadium-chromium-titanium waste salt in chlor-alkali |
| CN114293207A (en) * | 2021-11-19 | 2022-04-08 | 宁夏金昱元能源化学有限公司 | System and method for decomposing chlorate in caustic soda production by ion-exchange membrane method |
-
2008
- 2008-06-11 CN CN2008100499974A patent/CN101293661B/en not_active Expired - Fee Related
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|---|---|
| CN101293661A (en) | 2008-10-29 |
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