CN1267364C - Method and apparatus for preparing pure water by continuous electricity deionizing - Google Patents
Method and apparatus for preparing pure water by continuous electricity deionizing Download PDFInfo
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- CN1267364C CN1267364C CN 02153843 CN02153843A CN1267364C CN 1267364 C CN1267364 C CN 1267364C CN 02153843 CN02153843 CN 02153843 CN 02153843 A CN02153843 A CN 02153843A CN 1267364 C CN1267364 C CN 1267364C
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Abstract
The present invention relates to a method and an apparatus for preparing pure water by continuous electricity deionization. Four identical EDI apparatuses are used, wherein three EDI apparatuses are connected in series to prepare pure water, and another one EDI apparatus is used as the regeneration equipment of ion exchanger; three processes of ion exchange adsorption, ion orienting shift, and electrochemistry regeneration are respectively carried out in different EDI apparatuses so that the processes are operated at an optimal state. Compared with the existing EDI apparatus, the EDI apparatus of the present invention can use an equal phase ion exchange membrane, and can use a heterogeneous ion exchange membrane produced in China so that the manufacturing cost of EDI is obviously reduced. The present invention continuously and stably prepares pure water, and electricity consumption for preparing the water is greatly reduced.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of pure water, refer to produce the method for pure water especially with the continuous electrodeionization technology.
Background technology
Medicine, chemical industry and semicon industry need a large amount of pure water, and in the past few decades, the preparation of pure water mainly contains multistage distillation method and ion exchange method.Multistage distillation method energy consumption height, cost is also high; Ion exchange method can cause severe contamination to environment owing to need a large amount of acid base pair resins to regenerate.
In recent years, a kind of environmental protection system pure water technology-continuous electrodeionization technology (Electrodeionization that electrodialysis and ion-exchanger are organically combined, be called for short EDI) develop rapidly at western developed country, increase by geometric progression in the application of every field.China also presents the trend that increases rapidly to the application of EDI at present, however the ability that China does not also produce EDI equipment at present, the used whole dependence on import of EDI device; This is because China can not produce the required homogeneous ion-exchange membrane with high selection perviousness of EDI, can only produce and select the general heterogeneous ion-exchange membrane of through performance.The reason that heterogeneous ion-exchange membrane can not be used for EDI is because it selects perviousness than homogeneous ion-exchange membrane difference, ion migration of the same name or concentration diffusion phenomenon can occur under high potential difference or concentration difference situation, thereby cause ratio of desalinization to descend, and can't produce pure water.But the price of homogeneous ion-exchange membrane is than much higher times of heterogeneous ion-exchange membrane.
So-called EDI has loaded the yin, yang ion-exchanger at the freshwater room of electrodialyzer exactly.Because the conductive capability of pure water intermediate ion exchanger is than high 2～3 orders of magnitude of water, thereby the ion in the aqueous solution constantly with ion-exchanger exchange takes place and " ionic channel " by the exchanger formation enters dense chamber, the result increases the specific conductivity of freshwater room system (solution, exchanger and film) greatly, improve electrodialytic limiting current, reached highly desalination.When EDI overstepped the extreme limit electric current at running current, polarization and water decomposition can take place near the interfacial layer film and the exchanger, produced OH
-And H
+Ion, except that a part is migrated to dense hydroecium, major part will make the ion-exchanger conditioning in the freshwater room, keep its exchange capacity.The process that EDI removes effects of ion mainly comprises following three aspects:
(1) ion-exchange adsorption process: this process is by the exchange interaction of ion-exchanger to electrolyte ion in the water, to remove the ion in the water.(2) ion directional migration process: under the extra electric field effect, ionogen carries out selective migration by ion-exchanger and ion-exchange membrane in the water, thereby reaches the ionic effect of removing.(3) electrochemical regeneration process: the H that utilizes electrodialytic polarization and water decomposition to produce
+And OH
-Ion carries out electrochemical regeneration to the ion-exchanger that adsorbs after saturated.
Wherein preceding two processes all directly improve effluent quality, and owing to the ion-exchange meeting water quality are degenerated in the regenerative process.In theory, ion-exchange and electrochemical regeneration are two conflicting processes, therefore must select suitable working conditions, and these three processes are carried out respectively, so just can both satisfy the effluent quality requirement, can reach the regenerated purpose again.
But present EDI concentrates on ion-exchange absorption, ion directional migration, these 3 processes of electrochemical regeneration in one table apparatus when design simultaneously, in whole removal ionic process, light chamber is in from the feed-water end to the water side under the identical DC electric field effect all the time.This just makes EDI when operation, can not make these 3 processes all be in optimal operational condition simultaneously, common situation may be: voltage is not high when light chamber feed-water end needs high-voltage to carry out ion migration, or voltage is not low when needing low voltage to carry out ion-exchange absorption in water side, light chamber; Need the high-voltage voltage that is hydrolyzed when regenerating with electricity not high at light chamber feed-water end, or the intensive water decomposition but take place to need not the regenerated zone in water side, light chamber.
The external at present EDI equipment of producing all adopts homogeneous ion-exchange membrane, and the manufacturing cost height costs an arm and a leg.In addition, EDI equipment is easy to fouling, and influent quality is required very strictness, can occur energy consumption in use for some time and raise phenomenons such as effluent quality shakiness.All these have all limited popularization and the use of EDI in China.If ion-exchange absorption, ion directional migration, these 3 processes of electrochemical regeneration are carried out in different EDI devices respectively, then not only can obtain the pure water of continous-stable, and can also cut down the consumption of energy, also can reduce (can replace homogeneous ion-exchange membrane to make the EDI device) greatly to the ion-exchange membrane performance demands simultaneously, reduce manufacturing cost with heterogeneous ion-exchange membrane.
Summary of the invention
In view of defectives such as the existing manufacturing cost height of present EDI equipment, energy consumption height, easy fouling and effluent quality shakinesses, the purpose of this invention is to provide and a kind ofly can use homogeneous ion-exchange membrane, also can use heterogeneous ion-exchange membrane, simultaneously can also guarantee to produce continuously stable pure water, the method for the continuous electrodeionization system pure water that energy consumption is low and less scaling.
Technical scheme of the present invention is:
Whole continuous electrodeionization system pure water equipment comprises 4 identical EDI devices (being labeled as EDI1, EDI2, EDI3, EDI4 respectively), wherein 3 EDI device series connection are with the preparation pure water, that is: former water → EDI1 → EDI2 → EDI3 → pure water (or: former water → EDI1 → EDI2 → EDI4 → pure water), in addition 1 EDI device (EDI3 or EDI4) is as the reclaim equiment of ion-exchanger.
Former water at first enters EDI1, adds that at the electrode two ends of EDI1 (film is 1～2V) to voltage, and former water is carried out elementary desalination, removes most of electrolyte ion in the water for the voltage of medium tenacity; The light chamber water outlet of EDI1 enters EDI2, adds high strength voltage (film to voltage greater than 2V) at the electrode two ends of EDI2, and former water is carried out advanced desalination, and the electrolyte ion concentration in the water has been reduced to very low; The light chamber water outlet of EDI2 enters EDI3, the making alive not at the electrode two ends of EDI3, and the light chamber of EDI3 is done ion-exchange and is mixed bed and use, and by ion-exchanger residual electrolyte ion in the water is exchanged absorption, makes the light chamber water outlet of EDI3 reach the pure water quality.The major part of EDI3 light chamber water outlet is final pure water product, and sub-fraction enters EDI4 in addition.The pure water that enters EDI4 (film to voltage greater than 2V) under high strength of electric field take place intense hydrolysis from, produce a large amount of H
+And OH
-Ion is regenerated to the saturated ion-exchanger of absorption among the EDI4.
After the absorption of the ion-exchanger among the EDI3 was saturated, the EDI4 that is reproduced substituted, and EDI3 then is carried out electricity regeneration.After the ion-exchanger among EDI4 absorption was saturated, the EDI3 that then is reproduced substituted, EDI4 is carried out electricity regenerate, and like this circulation guaranteed that entire equipment can produce pure water continuously and stably.The mutual alternative of EDI3 and EDI4 mainly realizes manually or control automatically by threeway, valve and under meter.
Principle of the present invention can be illustrated as follows by Fig. 2 and Fig. 3:
As shown in Figure 2, the light chamber of EDI can be divided into 3 parts by water (flow) direction, and water inlet portion is called the I district, and the water part is called the III district, is called the II district at the transition portion of intaking with water outlet.
In the I district, contain a large amount of electrolyte ions in the solution, specific conductivity is higher.Because the permutoid reaction speed between ion and the exchanger 9 is exceedingly fast, the ion in the exchanger 9 rapid adsorbent solutions in the light chamber also is tending towards saturated, and under electric field action, ion migrates to dense chamber through exchanger 9 and film gradually; The ion that is not adsorbed in the solution then moves to cavity block 8 and anode membrane 10 respectively, and migrates to dense chamber through film.In the I district, because of all containing a large amount of transportable ions in solution and the exchanger 9, there are not polarization and water decomposition condition, the effect of exchanger 9 mainly is absorption and conduction.Only need the voltage of medium tenacity (film is 1～2V) can obtain higher ratio of desalinization to voltage in this district.
In the III district, water intermediate ion concentration is very low, therefore under the effect of electrical forces, between the ion-exchanger 9 and the contact part between exchanger 9 and the film because of polarization water decomposition takes place, H
+And OH
-Ionic concn raises rapidly in the part, and with exchanger 9 in the Me that adsorbed
+Or A
-Ion (Me
+Expression ionogen positively charged ion, A
-The expression electrolytic anion) ion-exchange takes place.Because ion exchange reaction speed will be much larger than the travelling speed of ion in exchanger 9, the therefore Me that is exchanged out
+And A
-Ion, major part come back in the solution of light chamber.This shows that in the III district, electrolyte ion generally can not reduce in the solution of light chamber, even may be because of the Me that exchanges out
+And A
-Ion and cause the rising of water concentration; Therefore in addition, the selection perviousness of ion-exchange membrane can not reach 100%, in III district, owing to concentration diffusion and ion be penetrated into light chamber from dense chamber also might cause the increase of water outlet intermediate ion sum and the rising of specific conductivity.The water decomposition in this district is unfavorable to improving effluent quality, should utilize 9 pairs of ionic adsorptive poweies of ion-exchanger to make water outlet up to standard under low voltage or no-voltage.
In the II district, ionic migration and water decomposition degree also fall between, and the effects of ion major part migrates to dense chamber through ion-exchanger 9, and this district has water decomposition to take place, but it is strong to be not so good as the III district.Can suitably increase voltage in this district and improve ratio of desalinization (film to voltage greater than 2V).
By the analysis in I, II, each district of III is found,, the voltage on film both sides certainly will to be improved if want to improve the ratio of desalinization in II district, this can make III district water decomposition increase, cause the energy consumption of EDI to increase, the rising of voltage simultaneously also will reduce the selection perviousness of ion-exchange membrane, make the water outlet water quality deterioration.If but, reduce film both sides voltage in order to satisfy the requirement in III district, and then the ratio of desalinization in I, II district descends, and I, II district elongate gradually, and shorten and final the disappearance gradually in the III district, can cause effluent quality to worsen equally.Therefore, in an EDI device, be difficult to satisfy ion-exchange absorption, ion directional migration, these 3 processes of electrochemical regeneration simultaneously, for this reason, we design technical process shown in Figure 3.
In technical process shown in Figure 3, EDI1 and EDI2 are equivalent to I, the II district among Fig. 2 respectively, and EDI2 voltage is higher than EDI1; EDI3 and EDI4 then are equivalent to mix bed and electric revivifier respectively in the different steps of flow process.
At starting stage Fig. 3 a, former water is after the desalination once more of the first desalination of EDI1 and EDI2, and the ion content in the water outlet of light chamber has been reduced to very low, and after EDI3 mixed bed absorption, water outlet can reach the effluent quality requirement of pure water fully again in the light chamber water outlet of EDI2.EDI4 is delivered in the part water outlet of EDI3, and the light chamber ion-exchanger to EDI4 under high voltage carries out electricity regeneration.
After the absorption of the ion-exchanger among the EDI3 was saturated, the EDI4 good with regeneration replaced EDI3, EDI3 carried out electricity regeneration, shown in Fig. 3 b.After the absorption of the exchanger among the EDI4 was saturated, the EDI3 good with regeneration replaced EDI4, EDI4 carried out electricity regeneration, shown in Fig. 3 a.So move in circles, can guarantee the quality and the continuity of water outlet.
The method of continuous electrodeionization system pure water of the present invention by ion-exchange absorption, 3 processes of ion directional migration and electrochemical regeneration are placed different EDI devices respectively, can make them all be under the optimum regime and move.Compare with present EDI equipment, EDI device of the present invention can use homogeneous ion-exchange membrane, also can use the home-made heterogeneous ion-exchange membrane, and the EDI manufacturing cost is significantly descended, and not only can produce pure water continuously and stably, and system water power consumption also reduces greatly.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is a device structure sketch of the present invention.
Fig. 2 is the zone chart of the light chamber of EDI along water (flow) direction.
Fig. 3 is a process flow sheet of the present invention.
1.EDI1 among the figure, 2.EDI2,3.EDI3,4.EDI4,5. threeway, 6. valve, 7. under meter, 8. anion-exchange membrane, 9. ion-exchanger, 10. cationic exchange membrane.
Embodiment
As shown in Figure 1, former water is pressed the different ratios preparation by tap water and distilled water, and used ion-exchange membrane is the home-made heterogeneous ion-exchange membrane.Former water at first enters EDI1, adds 18V voltage (film to voltage less than 2V) at the electrode two ends of EDI1, and former water is carried out elementary desalination; The light chamber water outlet of EDI1 enters EDI2, adds 25V (film to voltage greater than 2V) voltage at the electrode two ends of EDI2, and former water is carried out advanced desalination; The light chamber water outlet of EDI2 enters EDI3, the making alive not at the electrode two ends of EDI3, and the light chamber of EDI3 is equivalent to ion-exchange and mixes bed, by ion-exchanger residual electrolyte ion in the water is exchanged absorption, makes the light chamber water outlet of EDI3 reach the pure water quality.EDI3 light chamber water outlet distributes most of as final pure water product by threeway 5, valve 6 and under meter 7, sub-fraction enters EDI4 in addition.Add 30V (film to voltage greater than 2V) voltage at the electrode two ends of EDI4, the pure water that enters EDI4 under 30V voltage, take place intense hydrolysis from, produce a large amount of H
+And OH
-Ion is regenerated to the saturated ion-exchanger of absorption among the EDI4.
Table 1 has shown the experimental result under these processing condition.
The change of water quality of table 1 continuous electrodeionization system pure water technical process different steps
| Measure number of times | Specific conductivity μ s/cm | Ratio of desalinization % | |||
| Former water | EDI2 | | EDI2 | EDI3 | |
| 1 | 50.4 | 3.2 | 0.25 | 93.65 | 99.50 |
| 2 | 45.7 | 2.8 | 0.13 | 93.87 | 99.72 |
| 3 | 42.4 | 3.0 | 0.14 | 92.92 | 99.67 |
| 4 | 39.5 | 2.9 | 0.13 | 92.66 | 99.67 |
| 5 | 30.6 | 2.2 | 0.10 | 92.81 | 99.67 |
| 6 | 22.3 | 1.8 | 0.13 | 91.93 | 99.42 |
| 7 | 18.9 | 2.1 | 0.20 | 88.89 | 98.94 |
| 8 | 33.5 | 2.9 | 0.13 | 91.34 | 99.61 |
| 9 | 56.8 | 4.6 | 0.14 | 91.90 | 99.75 |
| 10 | 78.9 | 6.9 | 0.17 | 91.25 | 99.78 |
| 11 | 66.5 | 6.6 | 0.17 | 90.08 | 99.74 |
| 12 | 50.1 | 6.2 | 0.14 | 87.62 | 99.72 |
| 13 | 126.3 | 8.9 | 0.13 | 92.95 | 99.90 |
| 14 | 102.4 | 7.5 | 0.13 | 92.68 | 99.87 |
| 15 | 66.9 | 7.9 | 0.20 | 88.19 | 99.70 |
| 16 | 56.2 | 5.6 | 0.17 | 90.04 | 99.70 |
| 17 | 50.4 | 3.3 | 0.14 | 93.45 | 99.72 |
| 18 | 48.6 | 3.3 | 0.10 | 93.21 | 99.79 |
| 19 | 40.2 | 2.0 | 0.13 | 95.02 | 99.68 |
| 20 | 37.7 | 2.5 | 0.17 | 93.37 | 99.55 |
| 21 | 32.5 | 2.2 | 0.14 | 93.23 | 99.57 |
Claims (4)
1. the method for a continuous electrodeionization system pure water is characterized in that:
(1) whole process comprises EDI1 (1), EDI2 (2), EDI3 (3) and EDI4 (4) totally 4 EDI devices, and wherein the series connection of 3 EDI devices is with the preparation pure water, and 1 EDI device is as the electric reclaim equiment of ion-exchanger in addition;
(2) 3 prepared pure water of EDI device of connecting, most of pure water as final preparation, all the other sub-fractions are intake as other the light chamber of 1 EDI device:
(3) film of EDI1 (1) to voltage less than 2V, the film of EDI2 (2) to voltage greater than 2V, the film of EDI3 (3) and EDI4 (4) to voltage series connection as preparation during pure water voltage be 0, voltage is greater than 2V as the electric reclaim equiment of ion-exchanger the time;
(4) EDI3 (3) and EDI4 (4) exchange, i.e. after the absorption of ion-exchanger (9) in EDI3 (3) is saturated, substitute EDI3 (3) with regard to the EDI4 (4) after the electricity consumption regeneration, and EDI3 (3) is carried out electricity regeneration; After the absorption of the ion-exchanger (9) among the EDI4 (4) was saturated, then the EDI3 (3) after the electricity consumption regeneration replaced EDI4 (4), and EDI4 (4) is carried out electricity regeneration, so hockets.
2. continuous electrodeionization system pure water processes according to claim 1 is characterized in that: the mutual alternative of EDI3 (3) and EDI4 (4) realizes manually or control automatically by threeway (5), valve (6) and under meter (7).
3. continuous electrodeionization system pure water processes according to claim 1 is characterized in that: EDI is by electrode, anion and cation exchange membrane, the deep or light chamber dividing plate alternately arranged and be filled in light indoor ion-exchanger and constitute.
4. continuous electrodeionization system pure water processes according to claim 3 is characterized in that: the ion-exchange membrane of EDI can be homogeneous ion-exchange membrane or heterogeneous ion-exchange membrane; Ion-exchanger can be ion exchange resin or ion-exchange fiber.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02153843 CN1267364C (en) | 2002-12-05 | 2002-12-05 | Method and apparatus for preparing pure water by continuous electricity deionizing |
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|---|---|---|---|
| CN 02153843 CN1267364C (en) | 2002-12-05 | 2002-12-05 | Method and apparatus for preparing pure water by continuous electricity deionizing |
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|---|---|
| CN1504428A CN1504428A (en) | 2004-06-16 |
| CN1267364C true CN1267364C (en) | 2006-08-02 |
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|---|---|---|---|
| CN 02153843 Expired - Fee Related CN1267364C (en) | 2002-12-05 | 2002-12-05 | Method and apparatus for preparing pure water by continuous electricity deionizing |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442741A (en) * | 2010-10-09 | 2012-05-09 | 韦建敏 | 1+1 protection system for etching solution recycling equipment |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303008C (en) * | 2004-08-04 | 2007-03-07 | 同济大学 | Process for removing trace ammonia from high purity water |
| CN110066075A (en) * | 2019-05-29 | 2019-07-30 | 浙江大学 | The landfill leachate advanced treatment apparatus and its technique of in-situ regeneration granule electrode |
| CN112546673B (en) * | 2020-12-18 | 2022-07-08 | 欧尚元(天津)有限公司 | Parallel uniform-feeding resin column system and feeding control method |
-
2002
- 2002-12-05 CN CN 02153843 patent/CN1267364C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442741A (en) * | 2010-10-09 | 2012-05-09 | 韦建敏 | 1+1 protection system for etching solution recycling equipment |
| CN102442741B (en) * | 2010-10-09 | 2013-06-26 | 韦建敏 | 1+1 protection system for etching solution recycling equipment |
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| CN1504428A (en) | 2004-06-16 |
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