CN102021601A - Electrolytic process of mixed liquor of waste diluted hydrochloric acid - Google Patents
Electrolytic process of mixed liquor of waste diluted hydrochloric acid Download PDFInfo
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- CN102021601A CN102021601A CN 201010528518 CN201010528518A CN102021601A CN 102021601 A CN102021601 A CN 102021601A CN 201010528518 CN201010528518 CN 201010528518 CN 201010528518 A CN201010528518 A CN 201010528518A CN 102021601 A CN102021601 A CN 102021601A
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Abstract
一种稀废盐酸的混合液电解法，以稀盐酸溶解精制后的食盐至饱和得到电解质混合液；将混合液加热至30℃～90℃通过隔膜或阳离子膜电解槽，以铜网为阴极、钛合金为阳极，槽电压控制在1.9～3.2V、电流密度控制在1000～4000A/m2，得到氯气和氢气；电解采用连续多级的方式，即I级电解后的混合液再行补充精制食盐至饱和进行II级电解，II级电解后的混合液再行补充精制食盐至饱和进行III级电解，以此类推，直至混合液的pH＝3～5；电解完成后的混合液再补充食盐至饱和进入隔膜或离子膜电解槽进行正常的氯碱工业生产。本发明与氯碱工业相比，混合液电解制备氯气、氢气的槽电压低、电流效率高。本发明是企业生产所产生的稀废盐酸资源化最为有效的方法之一。A mixed solution electrolysis method of dilute waste hydrochloric acid. The diluted hydrochloric acid is used to dissolve refined salt to saturation to obtain an electrolyte mixed solution; the mixed solution is heated to 30°C-90°C and passed through a diaphragm or a cationic membrane electrolyzer, with a copper mesh as a cathode, Titanium alloy is used as the anode, the cell voltage is controlled at 1.9-3.2V, and the current density is controlled at 1000-4000A/m 2 to obtain chlorine and hydrogen; the electrolysis adopts a continuous multi-stage method, that is, the mixed solution after I-level electrolysis is supplemented and refined Salt is saturated to carry out level II electrolysis, and the mixed solution after level II electrolysis is supplemented with refined salt to saturation, and then level III electrolysis is performed, and so on, until the pH of the mixed solution is 3~5; after the completion of electrolysis, the mixed solution is supplemented with salt To saturation, enter the diaphragm or ion-exchange membrane electrolyzer for normal chlor-alkali industrial production. Compared with the chlor-alkali industry, the present invention has low cell voltage and high current efficiency for preparing chlorine gas and hydrogen gas by electrolysis of mixed solution. The invention is one of the most effective methods for resource recovery of dilute waste hydrochloric acid produced in enterprise production.
Description
Technical field
The present invention relates to a kind of method of resource of abraum salt acid, be specifically related to a kind of enterprise (as polyvinyl chloride, chlorinatedpolyethylene, tolylene diisocyanate, 4,4-two isocyano-diphenylol methane, Cellmic C 121 etc.) and produce the rare abraum salt mixed solution electrolytic process that is produced based on chlorine industry.
Background technology
Produce rare abraum salt acid (1%～15%) recycling that is produced based on the enterprise of chlorine industry and belong to global problem.Domestic certain chlorinatedpolyethylene enterprise (120,000 tons of CPE/a, its rare abraum salt acid yield 750m
3/ d) produce the dilute hydrochloric acid produced to be taken as acid waste water and after the neutralizing treatment of super-alkaline substance (Wingdale or carbide slag), to discharge, required expense is approximately 7,000,000 yuan (except effluent charge), this has not only increased the economical load of enterprise, and is the huge wasting of resources.Therefore, exploitation is fit to the dilute hydrochloric acid resource technology, realizes the zero release of dilute hydrochloric acid resource utilization and pollution, not only has good economic benefit, and promotes its energy-saving and emission-reduction, goes on the motorway of recycling economy.
The abraum salt acid recovery and the resource technology of bibliographical information divide two classes.One, rare abraum salt acid (containing a large amount of metal ions) of Steel Wire Products Industry is purpose to obtain concentrated hydrochloric acid, generally adopts extraction process, roasting method, method of evaporation etc.They are two years old, for the enterprise that uses chlorine to produce (as polyvinyl chloride, chlorinatedpolyethylene, tolylene diisocyanate, 4,4-two isocyano-diphenylol methane, Cellmic C 121 etc.), by product HCl gas that is produced or employing direct oxidation method or employing catalytic oxidation prepare chlorine, and the patent documentation and the research paper that relate to these two kinds of methods are existing both at home and abroad a lot.
Another kind of HCl gas method of resource is that water absorbs the hydrochloric acid that obtains higher concentration.Chlorine is under-supply because the hydrochloric acid supply is often excessive, can stands with concentrated hydrochloric acid electrolytic preparation chlorine and pays close attention to widely or practical application.The patent documentation of this respect, research paper, production practice are reported also a lot both at home and abroad, mainly carry out around reduction bath voltage, raising current efficiency, the concentration of electrolysis hydrochloric acid is generally more than 20%, do not see as yet and concentration is lower than 15% electrolysis of hydrochloric acid bibliographical information.
Summary of the invention
The object of the present invention is to provide a kind of enterprise (as polyvinyl chloride, chlorinatedpolyethylene, tolylene diisocyanate, 4,4-two isocyano-diphenylol methane, Cellmic C 121, hydrochloric acid etc.) to produce the mixed solution electrolytic process of the rare abraum salt acid that is produced based on chlorine industry.
For achieving the above object, the method that the present invention adopts is:
1) salt after refining is to the saturated ionogen mixed solution that obtains with diluted hydrochloric acid dissolution, and the concentration of HCl is 1%～15% in this mixed solution;
2) mixed solution being heated to 30 ℃～90 ℃ by barrier film or cationic membrane electrolyzer, is that negative electrode, titanium alloy are anode with the copper mesh, and bath voltage is controlled at 1.9～3.2V, current density is controlled at 1000～4000A/m
2, obtain chlorine and hydrogen;
3) mode of continuous multi-stage is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, mixed solution after the electrolysis of II level is gone post-refining salt again and is carried out the electrolysis of III level to saturated, by that analogy, and until pH=3～5 of mixed solution;
4) the mixed solution restock salt after electrolysis is finished enters barrier film or ion-exchange membrane electrolyzer carries out normal chlorine industry production to saturated.
The present invention compares with chlorine industry, and the bath voltage of mixed solution electrolytic preparation chlorine, hydrogen is low, current efficiency is high.The present invention is that enterprise produces the sour resource utilization of the rare abraum salt that is produced one of effective means the most.
Embodiment
Embodiment 1:
1) salt after refining is to the saturated ionogen mixed solution that obtains with diluted hydrochloric acid dissolution, and the concentration of HCl is 1% in this mixed solution;
2) mixed solution being heated to 60 ℃ by barrier film or cationic membrane electrolyzer, is that negative electrode, titanium alloy are anode with the copper mesh, and bath voltage is controlled at 1.9V, current density is controlled at 1000A/m
2, obtain chlorine and hydrogen, current efficiency (chlorine) 90～98%;
3) mode of continuous multi-stage is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, mixed solution after the electrolysis of II level is gone post-refining salt again and is carried out the electrolysis of III level to saturated, by that analogy, and until the pH=3 of mixed solution;
4) the mixed solution restock salt after electrolysis is finished enters barrier film or ion-exchange membrane electrolyzer carries out normal chlorine industry production to saturated.
Embodiment 2:
1) salt after refining is to the saturated ionogen mixed solution that obtains with diluted hydrochloric acid dissolution, and the concentration of HCl is 8% in this mixed solution;
2) mixed solution being heated to 30 ℃ by barrier film or cationic membrane electrolyzer, is that negative electrode, titanium alloy are anode with the copper mesh, and bath voltage is controlled at 3.2V, current density is controlled at 3000A/m
2, obtain chlorine and hydrogen, current efficiency (chlorine) 90～98%;
3) mode of continuous multi-stage is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, mixed solution after the electrolysis of II level is gone post-refining salt again and is carried out the electrolysis of III level to saturated, by that analogy, and until the pH=4 of mixed solution;
4) the mixed solution restock salt after electrolysis is finished enters barrier film or ion-exchange membrane electrolyzer carries out normal chlorine industry production to saturated.
Embodiment 3:
1) salt after refining is to the saturated ionogen mixed solution that obtains with diluted hydrochloric acid dissolution, and the concentration of HCl is 5% in this mixed solution;
2) mixed solution being heated to 90 ℃ by barrier film or cationic membrane electrolyzer, is that negative electrode, titanium alloy are anode with the copper mesh, and bath voltage is controlled at 2.5V, current density is controlled at 2000A/m
2, obtain chlorine and hydrogen, current efficiency (chlorine) 90～98%;
3) mode of continuous multi-stage is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, mixed solution after the electrolysis of II level is gone post-refining salt again and is carried out the electrolysis of III level to saturated, by that analogy, and until the pH=5 of mixed solution;
4) the mixed solution restock salt after electrolysis is finished enters barrier film or ion-exchange membrane electrolyzer carries out normal chlorine industry production to saturated.
Embodiment 4:
1) salt after refining is to the saturated ionogen mixed solution that obtains with diluted hydrochloric acid dissolution, and the concentration of HCl is 10% in this mixed solution;
2) mixed solution being heated to 50 ℃ by barrier film or cationic membrane electrolyzer, is that negative electrode, titanium alloy are anode with the copper mesh, and bath voltage is controlled at 2.8V, current density is controlled at 2600A/m
2, obtain chlorine and hydrogen, current efficiency (chlorine) 90～98%;
3) mode of continuous multi-stage is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, mixed solution after the electrolysis of II level is gone post-refining salt again and is carried out the electrolysis of III level to saturated, by that analogy, and until the pH=5 of mixed solution;
4) the mixed solution restock salt after electrolysis is finished enters barrier film or ion-exchange membrane electrolyzer carries out normal chlorine industry production to saturated.
Embodiment 5:
1) salt after refining is to the saturated ionogen mixed solution that obtains with diluted hydrochloric acid dissolution, and the concentration of HCl is 15% in this mixed solution;
2) mixed solution being heated to 70 ℃ by barrier film or cationic membrane electrolyzer, is that negative electrode, titanium alloy are anode with the copper mesh, and bath voltage is controlled at 3.0V, current density is controlled at 4000A/m
2, obtain chlorine and hydrogen, current efficiency (chlorine) 90～98%;
3) mode of continuous multi-stage is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, mixed solution after the electrolysis of II level is gone post-refining salt again and is carried out the electrolysis of III level to saturated, by that analogy, and until the pH=4 of mixed solution;
4) the mixed solution restock salt after electrolysis is finished enters barrier film or ion-exchange membrane electrolyzer carries out normal chlorine industry production to saturated.
The present invention is the enterprise on basis for chlorine industry, and it is produced rare abraum salt acid (need suitably the handle in case of necessity) place of water that is produced and makees solvent, and the salt after dissolving is refining is to the saturated ionogen mixed solution that obtains; Mixed solution is by barrier film (or ionic membrane) electrolytic tank electrolysis, and bath voltage, current density are controlled at suitable scope, obtain chlorine and hydrogen; Multistage successive mode (ensureing higher current efficiency) is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, the capable again post-refining salt of mixed solution after the electrolysis of II level carries out the electrolysis of III level by that analogy to saturated, until pH of mixed=3～7; Mixed solution restock salt after electrolysis is finished to saturated barrier film (or ionic membrane) electrolyzer that enters carries out normal chlorine industry production.Compare with chlorine industry, the bath voltage of mixed solution electrolytic preparation chlorine, hydrogen is low, current efficiency is high.The present invention's (technology) is that this type of enterprise produces the sour resource utilization of the rare abraum salt that is produced one of effective means the most.
Claims (1)
1. the mixed solution electrolytic process of rare abraum salt acid is characterized in that may further comprise the steps:
1) salt after refining is to the saturated ionogen mixed solution that obtains with diluted hydrochloric acid dissolution, and the concentration of HCl is 1%～15% in this mixed solution;
2) mixed solution being heated to 30 ℃～90 ℃ by barrier film or cationic membrane electrolyzer, is that negative electrode, titanium alloy are anode with the copper mesh, and bath voltage is controlled at 1.9～3.2V, current density is controlled at 1000～4000A/m
2, obtain chlorine and hydrogen;
3) mode of continuous multi-stage is adopted in electrolysis, it is the extremely saturated II of the carrying out level electrolysis of the capable again post-refining salt of mixed solution after the electrolysis of I level, mixed solution after the electrolysis of II level is gone post-refining salt again and is carried out the electrolysis of III level to saturated, by that analogy, and until pH=3～5 of mixed solution;
4) the mixed solution restock salt after electrolysis is finished enters barrier film or ion-exchange membrane electrolyzer carries out normal chlorine industry production to saturated.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010105285184A CN102021601B (en) | 2010-11-03 | 2010-11-03 | A mixed solution electrolysis method of dilute waste hydrochloric acid |
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| CN2010105285184A CN102021601B (en) | 2010-11-03 | 2010-11-03 | A mixed solution electrolysis method of dilute waste hydrochloric acid |
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| CN102021601A true CN102021601A (en) | 2011-04-20 |
| CN102021601B CN102021601B (en) | 2012-05-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205575A (en) * | 2013-03-05 | 2013-07-17 | 广州有色金属研究院 | Method for recovering hydrochloric acid and rare earth from oxalate rare earth precipitation waste water |
| CN112759036A (en) * | 2020-12-28 | 2021-05-07 | 云南驰宏国际锗业有限公司 | Method for treating hydrochloric acid wastewater by electrolysis method and electrolytic cell for hydrochloric acid wastewater electrolysis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4311568A (en) * | 1980-04-02 | 1982-01-19 | General Electric Co. | Anode for reducing oxygen generation in the electrolysis of hydrogen chloride |
| US5411641A (en) * | 1993-11-22 | 1995-05-02 | E. I. Du Pont De Nemours And Company | Electrochemical conversion of anhydrous hydrogen halide to halogen gas using a cation-transporting membrane |
| CN1554597A (en) * | 2003-12-26 | 2004-12-15 | 赵厚俊 | Method for treating waste water contaning sodium hydroxide and hydrochloric acid separately |
-
2010
- 2010-11-03 CN CN2010105285184A patent/CN102021601B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4311568A (en) * | 1980-04-02 | 1982-01-19 | General Electric Co. | Anode for reducing oxygen generation in the electrolysis of hydrogen chloride |
| US5411641A (en) * | 1993-11-22 | 1995-05-02 | E. I. Du Pont De Nemours And Company | Electrochemical conversion of anhydrous hydrogen halide to halogen gas using a cation-transporting membrane |
| CN1554597A (en) * | 2003-12-26 | 2004-12-15 | 赵厚俊 | Method for treating waste water contaning sodium hydroxide and hydrochloric acid separately |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205575A (en) * | 2013-03-05 | 2013-07-17 | 广州有色金属研究院 | Method for recovering hydrochloric acid and rare earth from oxalate rare earth precipitation waste water |
| CN112759036A (en) * | 2020-12-28 | 2021-05-07 | 云南驰宏国际锗业有限公司 | Method for treating hydrochloric acid wastewater by electrolysis method and electrolytic cell for hydrochloric acid wastewater electrolysis |
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| CN102021601B (en) | 2012-05-23 |
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