CN103114298A - Membrane distillation (MD) coupled alkali preparation technique - Google Patents
Membrane distillation (MD) coupled alkali preparation technique Download PDFInfo
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- CN103114298A CN103114298A CN2013100545988A CN201310054598A CN103114298A CN 103114298 A CN103114298 A CN 103114298A CN 2013100545988 A CN2013100545988 A CN 2013100545988A CN 201310054598 A CN201310054598 A CN 201310054598A CN 103114298 A CN103114298 A CN 103114298A
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Abstract
The invention provides a membrane distillation (MD) coupled alkali preparation technique. By utilizing the MD method, the MD coupled alkali preparation technique can economically and effectively concentrate light salt brine without adding vapor, electricity or any other energy source, and the concentrated light salt brine has qualified sodium chloride content, and can directly return to the electrolytic bath system to be reutilized. The invention uses a novel full-closed-loop small-circulation technique instead of the traditional quasi-closed-loop large-circulation technique, optimizes the circulation links of the perhalogenation method, and changes the irrationality in the existing ion membrane alkali preparation technique. Thus, the invention can implement energy saving and emission reduction, reduce the production cost by one half, increase the yield and effect, and recycle the resources.
Description
Technical field
The present invention relates to industrial alkaline field, be specifically related to the membrane distillation concentration method of light salt brine, and a kind of ionic membrane method alkali-making process that is coupled.
Background technology
The traditional technology of ionic membrane method alkaline is the anolyte that contains NaCl210 ± 15g/L (being commonly called as in the industry " light salt brine ") with electrolyzer end discharge, and returning salt operation is added solid salt (or mixing halogen) preparation NaCl solution (280 ± 50g/L) again.Again successively through once, the secondary brine operation, enter electrolyzer.This is the closed circuit systemic circulation technique of a kind of irrational standard in essence.The enterprise of half stew in soy sauce alkali is more because needing the outsourcing solid salt to cause the rising of cost.
The enterprise of total halogenated caustic production is only also after light salt brine is carried out concentration and evaporation, the interflow primary brine.Still there is the unreasonable problem of technologic cyclic node, just save interpolation solid salt (or mixing halogen).And energy consumption is higher, and apparatus expensive is unfavorable to cost.
As seen, the technique of salt method and half halogen method alkaline is as the closed circuit systemic circulation technique of standard, though water yield balance, salt can not balance, replenishes outside the system that still needs, and also namely dissolves solid salt enrichment (mixing halogen, outsourcing salt is all also to freshen salt in essence); And the perhalogeno method is as circulation technology in the full cut-off road, and the concentrate light salt brine returns to primary brine process, then through exchange resin tower, secondary brine processed, this technique is unreasonable due to cyclic node, has strengthened the load of front end.
Recently, along with the raising of hot method evaporation technique, people begin to pay attention to repetition and the cascade utilization of steam latent heat and heat, the distillation (MVC) of calming the anger, function of mechanical steam recompression (MVR), and especially the latter, be present relatively best hot law technology.So some salt legal system alkali enterprise begins to attempt concentrated light salt brine, but uneconomical because of steam loss equally.Comparatively feasible (the application number: 200910192865.1) of not new MVR method only comparatively speaking.Though yet this method has realized the recycling of steam, high-order steam loss is still inevitable, and compression causes the loss of high-grade mechanical or electrical energy equally, and considers the corrosion-resistant titanium alloy equipment that adopts with heat exchange, is also that cost is expensive.
Therefore, break through traditional production model, seek economical and effective concentration method and the more rational novel process for making alkaline of technique for light salt brine, have very important production practice meaning.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of production of ion-exchange-membrane caustic soda, and for realizing that this technique needs a kind of cost-effective light salt brine concentration technique of coupling.
Light salt brine can directly return to electrolyzer recycling, dissolves solid salt and needn't get back to front end, or incorporates bittern, halogen ore deposit into; Also needn't return to primary brine workshop section as total halogenated caustic production enterprise, enter again electrolyzer after exchange resin tower; Light salt brine is through effective enrichment, and quality reaches returns to electrolyzer after refining secondary brine standard; But not will reduce the light salt brine of concentration in conventional ion embrane method alkali-making process, know the real situation for realizing that temperature, concentration evenly distribute etc., and directly return groove, the groove internal recycle that participates in.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of membrane distillation coupling alkali-making process, concrete steps are:
(1) collect the light salt brine that in electrolyzer, electrolysis treatment shifts out, this light salt brine concentration is 210 ± 15g/L;
(2) light salt brine that is 210 ± 15g/L with concentration in step (1) is sent into the MD assembly, concentrates by the MD method, is separated into sodium chloride solution and desalination pure water that concentration is 280 ± 50g/L;
(3) concentration of step (2) being made is that the sodium chloride solution of 280 ± 50g/L shifts out the MD assembly, directly returns to the electrolyzer system recycling.
The finished product are at electric tank cathode district end, occur with 32% the caustic soda form that can sell.
The MD assembly is the tunica fibrosa integrated system that uses the MD technology; The MD method is take vapor-liquid equilibrium as foundation, rely on vaporization heat to realize phase transformation, water in hot side light salt brine can be under the situation of normal pressure lower than boiling point, see through fenestra after vaporization, the gas phase that enters cold side is distillated after condensation, component is that it is at the steam pressure difference of film both sides by the impellent of film, resistance can be regarded membrane resistance as, due to disengaging of solvent, thereby original solution concentration is increased.
Preferably, above-mentioned membrane distillation coupling alkali-making process, the processing that light salt brine in described step (1) is removed sulfate radical.
Preferably, above-mentioned membrane distillation coupling alkali-making process, the concentrate salt solution described in described step (2) after the MD method is concentrated, concentration is in the 230-330g/L scope.
Preferably, above-mentioned membrane distillation coupling alkali-making process, the concentrate salt solution after MD method described in described step (2) is concentrated, concentration is in the 280-320g/L scope.
Preferably, above-mentioned membrane distillation coupling alkali-making process, described in described step (2), the MD assembly material has good anti-chlorine, heatproof, resistance to oxidation, corrosion resistance nature, and tunica fibrosa used is polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF) (PVDF), perfluoroethylene-propylene (FEP) or polypropylene (PP) hydrophobic hollow fiber film.
Preferably, above-mentioned membrane distillation coupling alkali-making process, described in described step (2) in the MD assembly tunica fibrosa be PVDF.
Preferably, above-mentioned membrane distillation coupling alkali-making process, described in described step (2), the MD method includes but not limited to the DCMD(direct contact membrane distillation), VMD(decompression or vacuum membrane distillation), the distillation of AGMD(gap membrane), SGMD(sweep gas membrane distillation), MEMD(multiple-effect membrane distillation).
Preferably, above-mentioned membrane distillation coupling alkali-making process, in described step (2), the MD method is VMD.
Above-mentioned membrane distillation coupling alkali-making process, can be used for of the desalination pure water salt operation that obtains in described step (2) or other are more helpful.Can be used for the cleaning of ion exchange resin; The flushing of electrolyzer; Open, when stopping to the protection of electrolyzer, ionic membrane; The startup of catholyte.
Beneficial effect of the present invention is really:
Above-mentioned membrane distillation coupling alkali-making process utilizes the MD method, can concentrate cost-effectively light salt brine, need not to add steam, electric equal energy source, and makes the content of sodium-chlor in light salt brine after concentrated up to standard, can directly return to electrolyzer system and recycle; This technique becomes traditional accurate closed circuit systemic circulation technique and is full cut-off road partial circulating novel process, optimize the cyclic node of perhalogeno method technique, changed the technique irrationality of existing ionic membrane method alkaline, not only can save energy reduction of discharging, production cost reduces by half, also can increase production and improve productivity, resources circulation.
Description of drawings
Fig. 1 is the schema of membrane distillation coupling alkali-making process of the present invention;
Fig. 2 is the sketch of membrane distillation coupling novel process for making alkaline.
Embodiment
In order to make those skilled in the art understand better technical scheme of the present invention, below in conjunction with the drawings and the specific embodiments, technical scheme of the present invention is described in further detail.
Embodiment 1
(1) adopting industrial sea salt is raw material, be that concentration is the sodium chloride solution of 305g/L with preparation of raw material, pass through afterwards pre-treatment, remove insoluble impurity and hardness ions, entering afterwards electrolytic tank electrolysis separates, chlorion wherein is with the form electrolytic separation of chlorine, and sodium ion separates through ionic membrane with the sodium hydroxide form; Solution after electrolysis can partly shift out outside electrolyzer by ionic membrane, to guarantee the concentration of solution in electrolyzer, collects the light salt brine that in electrolyzer, electrolysis treatment shifts out, and this light salt brine concentration is 210g/L;
(2) concentration in step (1) is sent into the MD assembly for the light salt brine of 210g/L, concentrate by VMD, in described MD assembly, tunica fibrosa is PVDF, be separated into sodium chloride solution and desalination pure water that concentration is 300g/L, for carrying out better electrolysis treatment, can be according to the preferred controlled concentration of actual condition;
(3) concentration of step (2) being made is that the sodium chloride solution of 300g/L shifts out the MD assembly, returns to the anode electrolytic cell district; Simultaneously, salt legal system alkali enterprise can return to front end salt operation with the desalination pure water, dissolves solid salt or is used for that other are more helpful; Total halogenated caustic production enterprise can be more helpful for other with the desalination pure water; The concentrate salt solution of MD assembly end output can with advance the secondary brine that needs before groove to heat and carry out heat exchange and process, with reasonable energy utilization better.
Embodiment 2
(1) adopting industrial sea salt is raw material, be that concentration is the sodium chloride solution of 300g/L with preparation of raw material, pass through afterwards pre-treatment, remove insoluble impurity and hardness ions, entering afterwards electrolytic tank electrolysis separates, chlorion wherein is with the form electrolytic separation of chlorine, and sodium ion separates through ionic membrane with the sodium hydroxide form; Solution after electrolysis can partly shift out outside electrolyzer by ionic membrane, to guarantee the concentration of solution in electrolyzer, collects the light salt brine that in electrolyzer, electrolysis treatment shifts out, and light salt brine is removed sulfate radical process, and this light salt brine concentration is 200g/L;
(2) with concentration in step (1) for to send into the MD assembly for the light salt brine of 200g/L, concentrate by DCMD, in described MD assembly, tunica fibrosa is PP, is separated into the sodium chloride solution that concentration is 290g/L and desalinates pure water;
(3) concentration of step (2) being made is that the sodium chloride solution of 290g/L shifts out the MD assembly, is undertaken shifting out the MD assembly after concentration detects by proofing unit, returns to the anode electrolytic cell district.
Above-mentioned detailed description of this a kind of membrane distillation coupling alkali-making process being carried out with reference to embodiment; illustrative rather than determinate; can list several embodiment according to institute's limited range; therefore in the variation and the modification that do not break away under general plotting of the present invention, within should belonging to protection scope of the present invention.
Claims (7)
1. a membrane distillation coupling alkali-making process, is characterized in that, concrete steps are:
(1) to the light salt brine of ion-exchange membrane electrolyzer positive column end output, carry out membrane distillation concentration and process;
(2) the concentrate salt solution after membrane distillation concentration directly returns to the electrolyzer system recycling.
2. membrane distillation according to claim 1 coupling alkali-making process is characterized in that: in described step (1), the light salt brine concentration of anode electrolytic cell district end output is 210 ± 15g/L.
3. membrane distillation according to claim 1 coupling alkali-making process, it is characterized in that: described step is carried out the removal of sulfate ion to light salt brine in (2).
4. membrane distillation according to claim 1 coupling alkali-making process, it is characterized in that: the concentrate salt solution in described step (1) after membrane distillation concentration, concentration is in the 230-330g/L scope.
5. membrane distillation according to claim 1 coupling alkali-making process is characterized in that: the desalination pure water of membrane distillation by-product in described step (1), can be used as salt pure water can be used for also that other are more helpful.
6. membrane distillation according to claim 1 coupling alkali-making process, it is characterized in that: in described step (1), membrane distillation assembly material used has good anti-chlorine, heatproof, resistance to oxidation, corrosion resistance nature.
7. membrane distillation according to claim 1 coupling alkali-making process, it is characterized in that: the membrane distillation method (MD) in described step (1) includes but not limited to, direct contact membrane distillation, decompression or vacuum membrane distillation, gap membrane distillation, sweep gas membrane distillation, multiple-effect membrane distillation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310054598.8A CN103114298B (en) | 2013-02-20 | 2013-02-20 | A kind of film distillation coupling alkali-making process |
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| CN201310054598.8A CN103114298B (en) | 2013-02-20 | 2013-02-20 | A kind of film distillation coupling alkali-making process |
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| CN103114298B CN103114298B (en) | 2016-05-11 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104928715A (en) * | 2015-05-26 | 2015-09-23 | 南通星球石墨设备有限公司 | Electrolyte recycling system for caustic soda production |
| CN111151140A (en) * | 2020-01-20 | 2020-05-15 | 河北工业大学 | Method for concentrating chlor-alkali anode dilute brine |
| CN112981457A (en) * | 2021-02-04 | 2021-06-18 | 广西田东锦盛化工有限公司 | Pure water recycling device in chlor-alkali production |
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| US5965004A (en) * | 1996-03-13 | 1999-10-12 | Sterling Pulp Chemicals, Ltd. | Chlorine dioxide generation for water treatment |
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2013
- 2013-02-20 CN CN201310054598.8A patent/CN103114298B/en not_active Expired - Fee Related
Patent Citations (5)
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| US5965004A (en) * | 1996-03-13 | 1999-10-12 | Sterling Pulp Chemicals, Ltd. | Chlorine dioxide generation for water treatment |
| CN1180874C (en) * | 1999-05-27 | 2004-12-22 | 荷兰应用科学研究会(Nto) | Method for the purification of a liquid by membrane distillation, in particular for the production of desalinated water from seawater or brackish water or process water |
| CN101653697A (en) * | 2004-06-04 | 2010-02-24 | 阿克科瓦尔内尔加拿大公司 | Apparatus and method for osmotic membrane distillation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104928715A (en) * | 2015-05-26 | 2015-09-23 | 南通星球石墨设备有限公司 | Electrolyte recycling system for caustic soda production |
| CN111151140A (en) * | 2020-01-20 | 2020-05-15 | 河北工业大学 | Method for concentrating chlor-alkali anode dilute brine |
| CN111151140B (en) * | 2020-01-20 | 2021-10-15 | 河北工业大学 | Method for concentrating chlor-alkali anode dilute brine |
| CN112981457A (en) * | 2021-02-04 | 2021-06-18 | 广西田东锦盛化工有限公司 | Pure water recycling device in chlor-alkali production |
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