CN101402497A - Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater - Google Patents
Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater Download PDFInfo
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- CN101402497A CN101402497A CNA2008102222805A CN200810222280A CN101402497A CN 101402497 A CN101402497 A CN 101402497A CN A2008102222805 A CNA2008102222805 A CN A2008102222805A CN 200810222280 A CN200810222280 A CN 200810222280A CN 101402497 A CN101402497 A CN 101402497A
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Abstract
The invention discloses an electrically deionized treatment method for recovering inorganic ammonia nitrogen wastewater. The method consists of the following steps: 1. pre-treatment is performed, an ion exchange calcium remover is additionally arranged, so that the water quality of discharged water is as follows: the SDI is less than or equal to 5, the hardness is less than or equal to 1mg/L, the turbidity is less than or equal to 1NTU, and the COD is less than or equal to 1mg/L; 2. first-level electrically deionized device is used, the water generated by the first-level electrically deionized device is pure water for process, and can be recycled; and by adopting the overflow concentrated method, the weight concentration of the ammonia salt of the cyclic concentrated water reaches 1 percent; and 3. a second-level electrically deionized device is used, the two electrically deionized devices are connected in series, the first-level concentrated water entering a fresh water chamber is desalted for reutilization; and by adopting the overflow concentrated method again, the weight concentration of the ammonia salt of the cyclic concentrated water reaches more than 10 percent, and the concentrated water is concentrated to obtain ammonia salt products. The method not only meets the zero discharge requirement on the system, but also reclaims the ammonia salt concentrated water and obtains the pure water for process; moreover, the method also has the advantages of advanced process, low cost, low energy consumption and simple operation.
Description
Technical field
The technology of the present invention field relates to inorganic ammonia nitrogen Wastewater Recovery, particularly utilizes the electrodeionization membrane technique that chemical fertilizer, chemical industry are produced inorganic ammonia nitrogen waste water and handle, and reclaims ammonium salt class industrial chemicals and obtains the technology pure water, realizes wastewater zero discharge.
Background technology
In the production process of chemical fertilizer and chemical enterprise, especially, produced a large amount of inorganic ammonia nitrogen waste waters in the enterprise that produces technologies such as ammonium chloride, ammonium nitrate, ammonium sulfate, not only waste industrial chemicals, and polluted environment.This inorganic ammonia nitrogen waste water is acid, and corrodibility is strong, and very difficult with treatment process recovery commonly used, biological oxidation process can only can not reclaim ammonia nitrogen oxidation in the waste water at all; Ion exchange method can reclaim ammonium salt then needs frequent regeneration; Reverse osmosis membrane technology can be separated the industrial chemicals in the waste water, and can make process water, but the water rate of recovery of reverse-osmosis treated is lower, its concentrated water drainage is high-volume high, when waste water ammonium salt concentration is low, need multistage reverse osmosis membrane processing, just can make the ammonium salt in the inorganic ammonia nitrogen waste water obtain reclaiming, increased the cost of handling waste water widely.Electroosmose process also can recycle waste water, but when handling low concentration waste water, easily produces concentration polarization, and power consumption increases greatly, has increased working cost.Therefore the technology of developing a kind of energy inorganic ammonia nitrogen waste water that handling property is good, cost is low is imperative.
The electrodeionization technology is a kind of new membrane technology that obtains industrialization in recent years, the electrodeionization technology is the product that electrodialysis and ion-exchange organically combine, and has prepared in the pure water in industries such as electronics, electric power, pharmacy and chemical industry to be promoted the use of (replacing original mixed bed with electric deionizer).Electrodeionization is called packed-bed electrodialysis again, illustrates that it grows up on the electrodialysis basis, and the performance of electric deionizer is better than the common electrical dialyzer, and the membrane area of electric deionizer is little, and resistance is little, power consumption is low, efficient is high.Electric deionizer is compared with ion-exchanger, and electric deionizer moves continuously, equipment usefulness not, need not to use acid-alkali regeneration, and environmental benefit is good.
The electrodeionization technology not only is used for pure water preparation, and can be applicable to the recovery of softening water preparation and heavy metal wastewater thereby, thereby expand to very high tap water of ion content and wastewater application field from the few pure water Application Areas of ion content, expand to ionic membrane from the ionic membrane separation field and concentrate the field.Therefore, having invented on electrodeionization soft water technology and the electrodeionization recovery heavy metal wastewater thereby technical foundation,, method and device that a kind of electrodeionization reclaims inorganic ammonia nitrogen waste water are proposed at the characteristics of inorganic ammonia nitrogen waste water and the deficiency of existing recovery method.
Summary of the invention
A kind ofly reclaim the electrodeionization treatment process that inorganic ammonia nitrogen waste water is used, form by following processing step:
(1) pre-treatment
In waste water tank 1, through pre-treatment, the ion-exchange deliming device 3 by setting up is removed calcium ions and magnesium ions residual in this waste water again, makes effluent quality reach SDI≤5, hardness≤1mg/L, turbidity≤1NTU, COD≤1mg/L with inorganic ammonia nitrogen wastewater collection;
(2) first step electrodeionization is handled
The inorganic ammonia nitrogen waste water that meets above-mentioned requirements through pre-treatment, enter first step electric deionizer, waste water flows into each freshwater room that is arranged in parallel membrane stack 6 respectively, under the DC electric field effect, and the ammonium salt ion in this waste water, migrate to each dense hydroecium 7 through ion-exchange membrane, and the technology pure water that obtains simultaneously flows out from freshwater room 6 outlets, is collected in the pure water jar 8, by pure water jar 8 outlet pure water output tubes 9, deliver to the process system reuse;
The inorganic ammonia nitrogen waste water of another strand, enter the dense water pot 5 of first step electric deionizer, enter the dense hydroecium 7 of each membrane stack that is arranged in parallel through water pump, its water outlet is back into dense water pot 5, so circulate, concentrated solution betaine mass concentration reaches 1% in dense water pot 5;
(3) second stage electrodeionization is handled
The ammonium salt mass concentration of extracting out from the dense water pot 5 of first step electric deionizer reaches 1% concentrated solution, through water pump send into preceding group of second stage electric deionizer each be arranged in parallel the freshwater room 12 of membrane stack, each is arranged in parallel the freshwater room 14 of membrane stack to flow into the back group again, under the effect of DC electric field, the ammonium salt ion of this concentrated solution migrates to each dense hydroecium 13 and 15 respectively through ion-exchange membrane, and the waste water that contains residual ammonium salt confluxes to waste water tank 1 from each freshwater room 14 outlets;
The ammonium salt mass concentration is 1% condensed water, go into the dense water pot 10 of second stage electric deionizer from dense water pot 5 overflows of first step electric deionizer, the dense hydroecium 13 of each membrane stack of group before water pump is sent into second stage electric deionizer earlier, and then the dense hydroecium 15 of inflow back each membrane stack of group, its water outlet is back into dense water pot 10, so circulate, concentrated solution betaine mass concentration reaches more than 10% in dense water pot 10, upflow tube 11 from dense water pot 10 flows out again, concentrate for circulation evaporator, obtain ammonium salt product.
The scope that the present invention reclaims ammonium salt mass concentration in the inorganic ammonia nitrogen waste water is 0.03%～3%.
Above-mentioned steps of the present invention (2) and (3) described electric deionizer are to reclaim the ammonia nitrogen waste water special use, its utmost point hydroecium does not partly communicate with dense hydroecium and other membrane stacks, utmost point hydroecium has special flowing water cooling loop, and utmost point hydroecium current flow from bottom to top, are beneficial to exhaust and cooling; Do not fill out electroconductive resin in the dense hydroecium, and the ion exchange resin of in freshwater room, filling, different and difference to some extent can be used the yin, yang hybrid resin to ammonium nitrate according to desire recovery ammonium salt, and ammonium chloride, volatile salt, bicarbonate of ammonia, ammonium sulfate and monoammonium sulfate then are advisable with single positive resin; The interior water (flow) direction of dense in the electric deionizer, freshwater room is an adverse current.
The described deliming device of above-mentioned steps of the present invention (1) is NH
4Type ion-exchanger, its regeneration system rapidly are open, can discharge the sewage that contains calcium ions and magnesium ions on a small quantity from blow-off pipe 4 as required.
Positively effect of the present invention is:
(1) treatment process advanced person of the present invention effectively reduces processing cost.Because the present invention adopts electrodeionization to separate and concentrates membrane technique, the ratio of desalinization of this device and the rate of recovery of water are higher than electrodialysis and reverse osmosis membrane technology, therefore the efficient height of handling.Used membrane stack is injection molded with macromolecular material, and alloy material that need not be special is corrosion-resistant, and selection is convenient, does not also adopt any chemical agent during processing, and equipment manufacturing cost and processing costs are reduced.
(2) save energy.Because the present invention adopts under DC electric field, realizes ion isolation and spissated electrodeionization technology, the condition that technological process takes place is a normal temperature, and therefore no phase transformation is compared with the distillation method of enrichment that produces phase transformation, cuts down the consumption of energy significantly
(3) reclaim ammonium salt concentrated solution and technology pure water simultaneously, realize waste water reclaiming, source of pollution have been stopped in the sewage recovering system zero release, and ecotope is protected, environmental protection and good in economic efficiency.
(4) simple to operate, improved the productive labor environment, realize cleaning and carry out production strictly in line with rules and regulations.
Description of drawings
Fig. 1: process flow sheet of the present invention;
Wherein, 1-waste water tank; The 2-pre-treatment;
3-deliming device; The 4-blow-off pipe;
The dense water pot of 5-first step electric deionizer; 6-first step electric deionizer membrane stack freshwater room;
The dense hydroecium of 7-first step electric deionizer membrane stack; 8-pure water jar;
9-pure water output tube; The dense water pot of 10-second stage electric deionizer;
11-concentrated solution output tube; Group membrane stack freshwater room before the electric deionizer of the 12-second stage;
The dense hydroecium of group membrane stack before the electric deionizer of the 13-second stage; Group membrane stack freshwater room behind the electric deionizer of the 14-second stage;
The dense hydroecium of group membrane stack behind the electric deionizer of the 15-second stage;
Fig. 2: reclaim the electrodeionization membrane stack synoptic diagram that the inorganic ammonia nitrogen waste water contain ammonium nitrate is used;
Wherein, 6-first step electric deionizer membrane stack freshwater room
(also representing to organize membrane stack freshwater room 12 and 14 before and after the electric deionizer of the second stage);
The dense hydroecium of 7-first step electric deionizer membrane stack
(also representing to organize the dense hydroecium 13 of membrane stack and 15 before and after the electric deionizer of the second stage);
16-electric deionizer membrane stack utmost point hydroecium;
Fig. 3: reclaim the electrodeionization membrane stack synoptic diagram that the inorganic ammonia nitrogen waste water contain other ammonium salts is used;
Wherein, 6-first step electric deionizer membrane stack freshwater room
(also representing to organize membrane stack freshwater room 12 and 14 before and after the electric deionizer of the second stage);
The dense hydroecium of 7-first step electric deionizer membrane stack
(also representing to organize the dense hydroecium 13 of membrane stack and 15 before and after the electric deionizer of the second stage);
16-electric deionizer membrane stack utmost point hydroecium.
Embodiment
With certain factory's ammonium chloride waste-water is example, the ammonium salt mass percentage concentration was 0.05% (belonging to the scope of application 0.03%～3% of the present invention) in the water, because this factory's process water is the reverse osmosis water, and do not pollute in the production process, entering waste water tank is the inorganic ammonia nitrogen waste water that cleans, can adopt simple pretreatment mode to handle, filter through active carbon adsorber earlier, remove anhydrate middle greasy dirt and organism, filter through 5 μ m security personnel strainer again, then by deliming device 3, make its water quality reach fouling factor SDI≤5, turbidity≤1.0NTU, hardness≤1mg/L, COD≤1mg/L;
Ion exchange resin adsorbs the calcium ions and magnesium ions in the water in the deliming device, after resin lost efficacy, recoil with pure water with technology earlier, to go out system just in case enter the mud and the impurity particle of system, be 10% ammonium salt concentrated solution with mass concentration during regeneration, regeneration waste liquid also can be discharged from blow-off pipe 4, moves thereby make closed circulation system reach no calcium, the impurity that enters system can in time be discharged, the safety of assurance system operation and reliable.
The used electric deionizer of the present invention is made up of several membrane stacks, and membrane stack is the minimum component units of electric deionizer.Membrane stack is formed (seeing Fig. 2 or Fig. 3) by several freshwater rooms 6 and dense hydroecium 7 and positive and negative electrode chamber, two ends 16 again, freshwater room 6 and dense hydroecium 7 and utmost point hydroecium all separate with ion-exchange membrane respectively, ion-exchange membrane can optionally see through ion, and water can not see through.
The special-purpose electric deionizer of the present invention is that film stacking structure is different with the difference of electric deionizer commonly used, from Fig. 2 and Fig. 3 as seen, its difference is: utmost point hydroecium 16 does not partly communicate with dense hydroecium 7 and other membrane stack, utmost point hydroecium has special flowing water cooling loop, utmost point hydroecium current flow from bottom to top, are beneficial to exhaust and cooling; Do not fill out electroconductive resin in the dense hydroecium 7, the ammonia nitrogen waste water (see figure 2) that recovery is contained ammonium nitrate, fill out the hybrid resin of negative resin (representing) and positive resin (representing) in the freshwater room 6 with black circle with white circle, to reclaiming the ammonia nitrogen waste water (see figure 3) of other ammonium salt, only fill out single positive resin (representing) in the freshwater room 6 with black circle; Current are counter-flow arrangement mutually in freshwater room 6 and the dense hydroecium 7, show with arrow on Fig. 2 and Fig. 3.
The present embodiment adopts the front and back stages electric deionizer, and the first step is used for inorganic ammonia nitrogen waste water with low concentration, and to be concentrated into the ammonium salt mass concentration be 1% concentrated solution, reclaims the technology pure water simultaneously; Second stage device is that 1% concentrated solution further is concentrated into more than 10% with the ammonium salt mass concentration, uses for extracting Chemicals.
First step electrodeionization is handled:
To meet 0.05% inorganic ammonia nitrogen waste water of above-mentioned requirements through pre-treatment, be divided into two strands, one current are sent into first step electric deionizer and are handled, current are arranged in parallel the freshwater room 6 of membrane stack by each, and under the DC electric field effect, the ammonium salt ion in this waste water migrates to each dense hydroecium 7 through ion-exchange membrane, and the technology that obtains simultaneously flows out from fresh water 7 outlets with pure water, be collected in the pure water jar 8,, deliver to the process system reuse by pure water jar 8 outlet pure water output tubes 9;
The inorganic ammonia nitrogen waste water of another strand, enter the dense water pot 5 of first step electric deionizer, enter the dense hydroecium 7 that each is arranged in parallel membrane stack through water pump, its water outlet so circulates back into dense water pot 5, form a closed cycle, dense hydroecium flow is 1: 9 with the ratio of freshwater room flow, and dense like this water circulation system and fresh-water system are divided open shop, along with the ammonium salt of freshwater room to continuous dense hydroecium migration, dense hydroecium ammonium salt concentration increases, and concentrated solution betaine mass concentration reaches about 1% in dense water pot 5;
Second stage electrodeionization is handled:
The ammonium salt mass concentration of extracting out from the dense water pot of first step electric deionizer 5 reaches 1% concentrated solution and is divided into two strands, one pump into preceding group of second stage electric deionizer each be arranged in parallel the freshwater room 12 of membrane stack, each is arranged in parallel the freshwater room 14 of membrane stack to flow into the back group again, under the effect of DC electric field, the ammonium salt ion of this concentrated solution migrates to each dense hydroecium 13 and 15 respectively through ion-exchange membrane, and the waste water that contains residual ammonium salt confluxes to waste water tank 1 from each freshwater room 15 outlets;
Another strand gone into the dense water pot 10 of second stage electric deionizer from dense water pot 5 overflows of first step electric deionizer, with unidirectional reverse checkvalve concentrated solution can oppositely do not flow backwards by dense water pot 5 to dense water pot 10.The group series connection is provided with each dense hydroecium 13 and 15 of membrane stack after water pump is sent into second stage electric deionizer, its water outlet is returning dense water pot 10, so circulate, form a closed cycle, dense hydroecium flow is 1: 9 with the ratio of freshwater room flow, in dense water pot 10, concentrated solution betaine mass concentration is reached more than 10%, concentrated solution output tube 11 from dense water pot 10 flows out again, concentrates for circulation evaporator, obtains ammonium salt product.
Reclaim the electrodeionization treatment process that inorganic ammonia nitrogen waste water uses and the application and the popularization of device, realize the zero release of sewage recovering system, both solve problem of environmental pollution, reclaimed ammonium salt industrial chemicals and technology pure water again, obtained the bumper harvests of economy and environmental benefit.Technology advanced person of the present invention, cost is low, and it is low, simple to operate to consume energy.
Claims (4)
1. one kind is reclaimed the electrodeionization treatment process that inorganic ammonia nitrogen waste water is used, and it is characterized in that following processing step:
(1) pre-treatment
In waste water tank 1, through pre-treatment, the ion-exchange deliming device 3 by setting up is removed calcium ions and magnesium ions residual in this waste water again, makes effluent quality reach SDI≤5, hardness≤1mg/L, turbidity≤1NTU, COD≤1mg/L with inorganic ammonia nitrogen wastewater collection;
(2) first step electrodeionization is handled
The inorganic ammonia nitrogen waste water that meets above-mentioned requirements through pre-treatment, enter first step electric deionizer, waste water flows into each freshwater room that is arranged in parallel membrane stack 6 respectively, under the DC electric field effect, and the ammonium salt ion in this waste water, migrate to each dense hydroecium 7 through ion-exchange membrane, and the technology pure water that obtains simultaneously flows out from freshwater room 6 outlets, is collected in the pure water jar 8, by pure water jar 8 outlet pure water output tubes 9, deliver to the process system reuse;
The inorganic ammonia nitrogen waste water of another strand, enter the dense water pot 5 of first step electric deionizer, enter a dense hydroecium 7 that is equipped with the individual membrane stack that is arranged in parallel through water pump, its water outlet is back into dense water pot 5, so circulate, concentrated solution betaine mass concentration reaches 1% in dense water pot 5;
(3) second stage electrodeionization is handled
The ammonium salt mass concentration of extracting out from the dense water pot 5 of first step electric deionizer reaches 1% concentrated solution, through water pump send into preceding group of second stage electric deionizer each be arranged in parallel the freshwater room 12 of membrane stack, each is arranged in parallel the freshwater room 14 of membrane stack to flow into the back group again, under the effect of DC electric field, the ammonium salt ion of this concentrated solution migrates to each dense hydroecium 13 and 15 respectively through ion-exchange membrane, and the waste water that contains residual ammonium salt confluxes to waste water tank 1 from each freshwater room 14 outlets;
The ammonium salt mass concentration is 1% condensed water, go into the dense water pot 10 of second stage electric deionizer from dense water pot 5 overflows of first step electric deionizer, the dense hydroecium 13 of each membrane stack of group before water pump is sent into second stage electric deionizer earlier, and then the dense hydroecium 15 of inflow back each membrane stack of group, its water outlet is back into dense water pot 10, so circulate, concentrated solution betaine mass concentration reaches more than 10% in dense water pot 10, upflow tube 11 from dense water pot 10 flows out again, concentrate for circulation evaporator, obtain ammonium salt product.
2. the electrodeionization treatment process of using according to the described recovery ammonia nitrogen waste water of claim 1 is characterized in that the scope of ammonium salt mass concentration in the described inorganic ammonia nitrogen waste water is 0.03%～3%.
3. the electrodeionization treatment process of using according to the described recovery ammonia nitrogen waste water of claim 1, it is characterized in that step (2) and (3) described electric deionizer are to reclaim the ammonia nitrogen waste water special use, its utmost point hydroecium does not partly communicate with dense hydroecium and other membrane stacks, utmost point hydroecium has special flowing water cooling loop, utmost point hydroecium current flow from bottom to top, are beneficial to exhaust and cooling; Do not fill out electroconductive resin in the dense hydroecium, and the ion exchange resin of in freshwater room, filling, the different and difference to some extent according to desire recovery ammonium salt can be used the yin, yang hybrid resin to ammonium nitrate, to ammonium chloride, volatile salt, bicarbonate of ammonia, ammonium sulfate and monoammonium sulfate, then use single positive resin; The interior water (flow) direction of dense in the electric deionizer, freshwater room is an adverse current.
4. the electrodeionization treatment process of using according to the described recovery ammonia nitrogen waste water of claim 1 is characterized in that the described deliming device of step (1) is NH
4Type ion-exchanger, its regeneration system rapidly are open, can discharge the sewage that contains calcium ions and magnesium ions on a small quantity from blow-off pipe 5 as required.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102222805A CN101402497A (en) | 2008-09-16 | 2008-09-16 | Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater |
| CN2009101775571A CN101648738B (en) | 2008-09-16 | 2009-09-15 | Electro-deionization method and electro-deionization device for recycling ammonia nitrogen waste water |
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| CNA2008102222805A CN101402497A (en) | 2008-09-16 | 2008-09-16 | Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater |
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| CNA2008102222805A Pending CN101402497A (en) | 2008-09-16 | 2008-09-16 | Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater |
| CN2009101775571A Active CN101648738B (en) | 2008-09-16 | 2009-09-15 | Electro-deionization method and electro-deionization device for recycling ammonia nitrogen waste water |
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| CN101830587A (en) * | 2010-04-26 | 2010-09-15 | 烟台大学 | Process and device for processing heavy metal wastewater |
| CN101648738B (en) * | 2008-09-16 | 2012-07-04 | 王方 | Electro-deionization method and electro-deionization device for recycling ammonia nitrogen waste water |
| CN103359854A (en) * | 2012-04-06 | 2013-10-23 | 王明亚 | Method and device for treating inorganic ammonium salt wastewater by using integrated membrane |
| CN104445755A (en) * | 2014-10-28 | 2015-03-25 | 中国科学院过程工程研究所 | Method for resourceful treatment of ammonia chloride wastewaters |
| CN104556314A (en) * | 2013-10-23 | 2015-04-29 | 苏州华清水处理技术有限公司 | Electrical deionization device for concentration during recycling of low-concentration ammonia-nitrogen wastewater |
| CN106315920A (en) * | 2016-09-23 | 2017-01-11 | 武汉兴天宇环境股份有限公司 | Method for treating middle and low-concentration ammonia-nitrogen wastewater |
| WO2017221199A1 (en) * | 2016-06-22 | 2017-12-28 | The Hong Kong Polytechnic University | Energy generation from pollutants |
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| JP3244404B2 (en) * | 1995-08-16 | 2002-01-07 | シャープ株式会社 | Water treatment method and water treatment device |
| KR100687095B1 (en) * | 2005-06-14 | 2007-02-26 | 한국전력기술 주식회사 | Reverse Electrodialysis-electrochemical Wastewater Treatment Process of Nitrogen Compounds |
| CN101402497A (en) * | 2008-09-16 | 2009-04-08 | 王方 | Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater |
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| CN103359854A (en) * | 2012-04-06 | 2013-10-23 | 王明亚 | Method and device for treating inorganic ammonium salt wastewater by using integrated membrane |
| CN104556314A (en) * | 2013-10-23 | 2015-04-29 | 苏州华清水处理技术有限公司 | Electrical deionization device for concentration during recycling of low-concentration ammonia-nitrogen wastewater |
| CN104445755A (en) * | 2014-10-28 | 2015-03-25 | 中国科学院过程工程研究所 | Method for resourceful treatment of ammonia chloride wastewaters |
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| CN101648738B (en) | 2012-07-04 |
| CN101648738A (en) | 2010-02-17 |
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