CN102515317A - Method and device for producing acid and ammonia water by using ammonia-nitrogen waste water - Google Patents
Method and device for producing acid and ammonia water by using ammonia-nitrogen waste water Download PDFInfo
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- CN102515317A CN102515317A CN2012100053921A CN201210005392A CN102515317A CN 102515317 A CN102515317 A CN 102515317A CN 2012100053921 A CN2012100053921 A CN 2012100053921A CN 201210005392 A CN201210005392 A CN 201210005392A CN 102515317 A CN102515317 A CN 102515317A
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- exchange membrane
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Abstract
The invention discloses a method and a device for producing acid and ammonia water by using ammonia-nitrogen waste water. According to the method and the device, an electrolytic cell is divided by a bipolar membrane, a cation-exchange membrane, an anion-exchange membrane and a bipolar membrane into three isolated chambers, the ammonia-nitrogen waste water is introduced into the isolated chamber between the anion-exchange membrane and the bipolar membrane, the electrolytic cell is energized, water is dissociated on the interface layer of the bipolar membrane to form H<+> and OH<->, NH4<4+> passes through the cation-exchange membrane to bond with the OH<-> to form ammonia water, and the acid radical passes through the anion-exchange membrane to form acid with H<+>. Compared with the prior art, the method and the device, which adopt a bipolar membrane electrodialysis process has the advantages of avoiding consuming acid, alkali and salt, avoiding producing waste liquid, achieving obvious environment and economic benefit, along with high integration degree, energy conservation and the like.
Description
Technical fieldThe present invention relates to processing method of industrial waste water, particularly relate to method for treating ammonia-nitrogen wastewater and device.
Background technologyAmmonia nitrogen waste water mainly shows two aspects for the harm of human and environment: first ammonia nitrogen is to health effects; Ammonia nitrogen in the water can convert nitrite under certain condition to; If long-term drinking; Nitrite in the water will become NSC 223080 with protein bound, and this is a kind of strong carcinogen, and is totally unfavorable to HUMAN HEALTH.It two is ammonia nitrogen influences to ecotope, and it mainly is free ammonia that ammonia nitrogen plays damaging effect to aquatic organism, and its toxicity is bigger tens times than ammonium salt, and increases with alkalescence.PH value and the water temperature of ammonia nitrogen toxicity and Chi Shui have substantial connection, and generally speaking, pH value and water temperature high toxicity more are strong more, to the similar nitrite of the harm of fish.Ammonia nitrogen has acute and chronic branch to the harm of aquatic organism.Chronic ammonia nitrogen is poisoned to endanger and is the reduction of ingesting, poor growth, tissue injury and the conveying of reduction oxygen between tissue.Fish are relatively more responsive to ammonia nitrogen in the water, but ammonia-nitrogen content Gao Shihui causes fish kills.Acute ammonia nitrogen poisons to endanger: aquatic organism shows as excited, and balance in water is twitched severe patient even death.Ammonia nitrogen has caused pollution to water body, makes fish kills, forms the health of nitrite harm humans.So ammonia nitrogen is an important indicator of estimating water pollution and " self-cleaning " situation.
The existing ammonia nitrogen waste water treatment process methods that add alkali ammonia still process that adopt do not reclaim and put into atmosphere more, and this is polluted-water not just, but still atmosphere pollution.
Summary of the inventionTechnical problem to be solved by this invention is to provide a kind of environment friendly and pollution-free method and device with ammonia nitrogen waste water production acid and ammoniacal liquor.
The present invention realizes through taking following technical scheme:
A kind of method of producing acid and ammoniacal liquor with ammonia nitrogen waste water is proposed; In electrolyzer; Be divided into three compartments with Bipolar Membrane, cationic exchange membrane, anion-exchange membrane and Bipolar Membrane successively, ammonia nitrogen waste water is fed in the compartment between anion-exchange membrane and the cationic exchange membrane; To the electrolyzer energising, dissociating of the interfacial layer generation water of Bipolar Membrane generates H
+And OH
-, NH
4 +Pass through cationic exchange membrane and OH
-In conjunction with forming ammoniacal liquor, acid ion passes through anion-exchange membrane and H
+Form acid.
Further, said ammonia nitrogen waste water contains ammonium chloride.
Further, said ammonia nitrogen waste water contains ammonium sulfate.
Further, said ammonia nitrogen waste water contains an ammonium nitrate.
Design, a kind of device made from ammonia nitrogen waste water production acid and ammoniacal liquor; Comprise ammonia nitrogen waste water circulation groove, electrolyzer, sour circulation groove and ammoniacal liquor circulation groove; Said electrolyzer is divided into three compartments with Bipolar Membrane, cationic exchange membrane, anion-exchange membrane and Bipolar Membrane successively; Said ammonia nitrogen waste water circulation groove communicates with compartment between anion-exchange membrane and the cationic exchange membrane; Said ammoniacal liquor circulation groove communicates with compartment between Bipolar Membrane and the cationic exchange membrane, and sour circulation groove communicates with compartment between Bipolar Membrane and the anion-exchange membrane.
Compared with prior art, the present invention adopts the bipolar membrane electrodialysis process, have the integrated level height, energy-conservation, do not consume any soda acid salt, do not produce technique effects such as waste liquid, environmental benefit and remarkable in economical benefits.
Description of drawings
Fig. 1 is the present invention produces acid and ammoniacal liquor with ammonia nitrogen waste water method and a device synoptic diagram.
EmbodimentBelow in conjunction with preferred embodiment the present invention is done further detailed description.
Present embodiment is to use ammonium chloride waste-water to be raw material production hydrochloric acid and ammoniacal liquor.As shown in Figure 1; Produce the device of acid and ammoniacal liquor with ammonia nitrogen waste water; Comprise electrolyzer, ammonia nitrogen waste water circulation groove, sour circulation groove and ammoniacal liquor circulation groove (ammonia nitrogen waste water circulation groove, sour circulation groove and ammoniacal liquor circulation groove are not shown in the figures), said electrolyzer is divided into three compartments with Bipolar Membrane BP, cationic exchange membrane A, anion-exchange membrane C and Bipolar Membrane BP successively.Said ammonia nitrogen waste water circulation groove communicates with compartment between anion-exchange membrane and the cationic exchange membrane; Ammonium chloride concentration electrolysis in the ammonia nitrogen waste water circulation groove is up to standard to emit during to emission concentration 10ppm; When not reaching emission concentration, electrolysis in the compartment between anion-exchange membrane and the cationic exchange membrane is delivered in circulation.Said ammoniacal liquor circulation groove communicates with compartment between Bipolar Membrane and the cationic exchange membrane; Ammonia concn in the ammoniacal liquor circulation groove surpasses 10%; Deliver to the production scene and use, ammonia concn does not reach at 10% o'clock, and then circulation is delivered in the compartment between Bipolar Membrane and the cationic exchange membrane.The acid circulation groove communicates with compartment between Bipolar Membrane and the anion-exchange membrane; Acid concentration in sour circulation groove surpasses 10%; Just deliver to the production scene and use, the acid concentration in the sour circulation groove does not reach 10%, in the compartment between the Bipolar Membrane that then circulates and the anion-exchange membrane.Bipolar Membrane is also claimed bipolar membrane, is specific ion exchange membrane, and it is by an anode membrane and the compounded yin, yang composite package of cavity block.The characteristics of this film are under the effect of DC electric field, the H between yin, yang film composite bed
2O is dissociated into H
+And OH
-And respectively through cavity block and anode membrane, as H
+And OH
-Ion source.Bipolar Membrane is divided by macroscopical film bulk structure can be divided into homogeneous phase Bipolar Membrane and out-phase Bipolar Membrane.
Ammonium chloride is the salts solution of easily ionizable, and the waste water that will contain ammonium chloride feeds the compartment between anion-exchange membrane and cationic exchange membrane.After applying direct current, the interfacial layer generation water of Bipolar Membrane (BP) dissociate positively charged ion NH
4 +Pass through the same OH of cationic exchange membrane C
-In conjunction with forming ammoniacal liquor, negatively charged ion Cl
-Pass through the same H of anion-exchange membrane
+In conjunction with forming hydrochloric acid.Reaction when Bipolar Membrane is dissociated: 2H
2O → 2H
++ 2OH
-Because H
2→ 2H
++ 2e, theoretical current potential are 0V; 2H
2O+2e → H
2↑+2OH
-, theoretical current potential is 0.828V, so this reaction potential is two reaction sum: 2H
2O → 2H
++ 2OH
-, theoretical current potential is 0.828V.And O is arranged
2And H
2The electrolysis theoretical voltage of water is 2.057V when separating out, and wherein the 1.229V voltage consumption is at O
2And H
2Generation on, the 0.828V voltage consumption is on the dissociation reaction of water.
Theoretical value needs the voltage of 0.828V to act on the Bipolar Membrane both sides, just can make water decomposition become H
+And OH
-, but actual existence owing to membrane resistance, interfacial layer resistance, actual potential is higher than theoretical value.However, Bipolar Membrane water decomposition method is produced soda acid and is still had clear superiority because it not energy expenditure in unwanted side reaction.Therefore have following advantage: handling for ammonia nitrogen waste water provides new thinking and terms of settlement, utilizes the combination of Bipolar Membrane and one pole film dexterously, and less energy-consumption ground changes ammonium chloride waste-water into hydrochloric acid and ammoniacal liquor is reused for the production scene; Process non-oxidation and reduction reaction; No side reaction product such as O
2And H
2Only need 1 counter electrode, practice thrift investment; Need not insert electrode at every compartment, device volume is little.
Instance: use the bipolar membrane electrodialysis device of specification as 300mm x 100mm; Totally 6 groups (1 pair of yin, yang film and 1 Bipolar Membrane are 1 group) membrane stacks, anode is that titanium is coated with ruthenium electrode, negative electrode is a stainless steel plate; Ammonium chloride solution is carried out the electrodialysis test; Process 10% hydrochloric acid and 10% ammoniacal liquor from 10% ammonium chloride solution, chloride solid power consumption 1600kwh per ton has obtained good effect.
Above content is to combine concrete optimal technical scheme to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (5)
1. method of producing acid and ammoniacal liquor with ammonia nitrogen waste water; It is characterized in that: in electrolyzer; Be divided into three compartments with Bipolar Membrane, cationic exchange membrane, anion-exchange membrane and Bipolar Membrane successively, ammonia nitrogen waste water is fed in the compartment between anion-exchange membrane and the cationic exchange membrane;
To the electrolyzer energising, dissociating of the interfacial layer generation water of Bipolar Membrane generates H
+And OH
-, NH
4 +Pass through cationic exchange membrane and OH
-In conjunction with forming ammoniacal liquor, acid ion passes through anion-exchange membrane and H
+Form acid.
2. method of producing acid and ammoniacal liquor with ammonia nitrogen waste water as claimed in claim 1, it is characterized in that: said ammonia nitrogen waste water contains ammonium chloride.
3. method of producing acid and ammoniacal liquor with ammonia nitrogen waste water as claimed in claim 1, it is characterized in that: said ammonia nitrogen waste water contains ammonium sulfate.
4. method of producing acid and ammoniacal liquor with ammonia nitrogen waste water as claimed in claim 1, it is characterized in that: said ammonia nitrogen waste water contains an ammonium nitrate.
5. device of producing acid and ammoniacal liquor with ammonia nitrogen waste water; It is characterized in that: comprise ammonia nitrogen waste water circulation groove, electrolyzer, sour circulation groove and ammoniacal liquor circulation groove; Said electrolyzer is divided into three compartments with Bipolar Membrane, cationic exchange membrane, anion-exchange membrane and Bipolar Membrane successively; Said ammonia nitrogen waste water circulation groove communicates with compartment between anion-exchange membrane and the cationic exchange membrane; Said ammoniacal liquor circulation groove communicates with compartment between Bipolar Membrane and the cationic exchange membrane, and sour circulation groove communicates with compartment between Bipolar Membrane and the anion-exchange membrane.
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|---|---|---|---|
| CN2012100053921A CN102515317A (en) | 2012-01-10 | 2012-01-10 | Method and device for producing acid and ammonia water by using ammonia-nitrogen waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100053921A CN102515317A (en) | 2012-01-10 | 2012-01-10 | Method and device for producing acid and ammonia water by using ammonia-nitrogen waste water |
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|---|---|
| CN102515317A true CN102515317A (en) | 2012-06-27 |
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| CN2012100053921A Pending CN102515317A (en) | 2012-01-10 | 2012-01-10 | Method and device for producing acid and ammonia water by using ammonia-nitrogen waste water |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787471A (en) * | 2014-01-24 | 2014-05-14 | 北京科技大学 | Device and method for processing sodium p-toluenesulfonate waste liquor |
| CN104291500A (en) * | 2014-11-13 | 2015-01-21 | 北京赛科康仑环保科技有限公司 | Resourceful treatment system of low-concentration NH4Cl wastewater containing Mo and method of resourceful treatment system |
| CN104355472A (en) * | 2014-10-28 | 2015-02-18 | 北京赛科康仑环保科技有限公司 | Inorganic ammonium salt-containing wastewater treatment system, treatment process and application of wastewater treatment system |
| CN105688676A (en) * | 2016-04-08 | 2016-06-22 | 中国科学院过程工程研究所 | Technique for preparing hypophosphorous acid through bipolar membrane electroosmosis method |
| WO2016131389A1 (en) * | 2015-02-16 | 2016-08-25 | 秦才东 | Method and device for exchanging and concentrating ion in solution |
| CN106380029A (en) * | 2016-11-30 | 2017-02-08 | 中国科学技术大学 | Integrated device of bipolar membrane electrodialysis and hollow fiber membrane contactor and method for wastewater deaminating |
| CN106999853A (en) * | 2014-10-09 | 2017-08-01 | 索尔维公司 | method for producing ammonia |
| CN107055884A (en) * | 2017-03-31 | 2017-08-18 | 常州大学 | A kind of nitrogen phosphorus waste water separating and treating apparatus |
| CN107055712A (en) * | 2017-05-05 | 2017-08-18 | 合肥工业大学 | A kind of method that utilization two benches bipolar membrane electrodialysis reclaims ammonia nitrogen, phosphorus and volatile fatty acid in feces of livestock and poultry hydrolyzate |
| CN109205941A (en) * | 2018-10-09 | 2019-01-15 | 浙江奇彩环境科技股份有限公司 | A kind of recycling processing method of high ammonia-nitrogen wastewater with high salt |
| CN110759554A (en) * | 2019-11-01 | 2020-02-07 | 扬州宏远电子股份有限公司 | Recycling and zero-discharge treatment method for ammonium adipate wastewater generated in aluminum foil formation |
| CN111892224A (en) * | 2020-08-07 | 2020-11-06 | 重庆大学 | Ammonia nitrogen wastewater treatment system and method based on south of road dialysis and osmotic distillation coupling |
| CN114956400A (en) * | 2022-06-01 | 2022-08-30 | 南京大学 | Device and method for recycling ammonia nitrogen in wastewater by electrochemical coupling solid electrolyte |
| CN115340166A (en) * | 2022-08-26 | 2022-11-15 | 中国科学院生态环境研究中心 | Flat-plate type membrane contact reactor and double-membrane wastewater deamination method |
| KR20230045665A (en) * | 2021-09-27 | 2023-04-05 | 한국에너지기술연구원 | multi-energy harvesting system |
| EP4442354A1 (en) | 2023-04-05 | 2024-10-09 | Evonik Operations GmbH | Recovery of ammonia and sulfuric acid from ammonium sulfate-rich (waste) waters |
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| CN1169121A (en) * | 1995-01-18 | 1997-12-31 | 埃勒夫阿托化学有限公司 | Regenerating acid, particularly strong organic acid, using bipolar membranes |
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Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787471B (en) * | 2014-01-24 | 2015-08-26 | 北京科技大学 | A kind of device and technique processing tosic acid waste liquor of sodium |
| CN103787471A (en) * | 2014-01-24 | 2014-05-14 | 北京科技大学 | Device and method for processing sodium p-toluenesulfonate waste liquor |
| CN106999853A (en) * | 2014-10-09 | 2017-08-01 | 索尔维公司 | method for producing ammonia |
| CN104355472A (en) * | 2014-10-28 | 2015-02-18 | 北京赛科康仑环保科技有限公司 | Inorganic ammonium salt-containing wastewater treatment system, treatment process and application of wastewater treatment system |
| CN104291500A (en) * | 2014-11-13 | 2015-01-21 | 北京赛科康仑环保科技有限公司 | Resourceful treatment system of low-concentration NH4Cl wastewater containing Mo and method of resourceful treatment system |
| CN104291500B (en) * | 2014-11-13 | 2016-04-13 | 北京赛科康仑环保科技有限公司 | A kind of lower concentration NH containing Mo 4the recycling treatment system of Cl waste water and method thereof |
| WO2016131389A1 (en) * | 2015-02-16 | 2016-08-25 | 秦才东 | Method and device for exchanging and concentrating ion in solution |
| CN105688676B (en) * | 2016-04-08 | 2018-04-03 | 中国科学院过程工程研究所 | The technique that a kind of bipolar membrane electrodialysis method prepares hypophosphorous acid |
| CN105688676A (en) * | 2016-04-08 | 2016-06-22 | 中国科学院过程工程研究所 | Technique for preparing hypophosphorous acid through bipolar membrane electroosmosis method |
| CN106380029A (en) * | 2016-11-30 | 2017-02-08 | 中国科学技术大学 | Integrated device of bipolar membrane electrodialysis and hollow fiber membrane contactor and method for wastewater deaminating |
| CN106380029B (en) * | 2016-11-30 | 2019-04-05 | 中国科学技术大学 | It is a kind of for the bipolar membrane electrodialysis of waste water deaminizing and the integrating device of hollow fiber membrane contactors and method |
| CN107055884A (en) * | 2017-03-31 | 2017-08-18 | 常州大学 | A kind of nitrogen phosphorus waste water separating and treating apparatus |
| CN107055712B (en) * | 2017-05-05 | 2020-06-05 | 合肥工业大学 | Method for recovering ammonia nitrogen, phosphorus and volatile fatty acid in livestock and poultry excrement hydrolysate by using two-stage bipolar membrane electrodialysis |
| CN107055712A (en) * | 2017-05-05 | 2017-08-18 | 合肥工业大学 | A kind of method that utilization two benches bipolar membrane electrodialysis reclaims ammonia nitrogen, phosphorus and volatile fatty acid in feces of livestock and poultry hydrolyzate |
| CN109205941A (en) * | 2018-10-09 | 2019-01-15 | 浙江奇彩环境科技股份有限公司 | A kind of recycling processing method of high ammonia-nitrogen wastewater with high salt |
| CN109205941B (en) * | 2018-10-09 | 2021-11-02 | 浙江奇彩环境科技股份有限公司 | Resourceful treatment method for high-salt high-ammonia nitrogen wastewater |
| CN110759554A (en) * | 2019-11-01 | 2020-02-07 | 扬州宏远电子股份有限公司 | Recycling and zero-discharge treatment method for ammonium adipate wastewater generated in aluminum foil formation |
| CN111892224A (en) * | 2020-08-07 | 2020-11-06 | 重庆大学 | Ammonia nitrogen wastewater treatment system and method based on south of road dialysis and osmotic distillation coupling |
| KR20230045665A (en) * | 2021-09-27 | 2023-04-05 | 한국에너지기술연구원 | multi-energy harvesting system |
| KR102652351B1 (en) * | 2021-09-27 | 2024-04-01 | 한국에너지기술연구원 | multi-energy harvesting system |
| CN114956400A (en) * | 2022-06-01 | 2022-08-30 | 南京大学 | Device and method for recycling ammonia nitrogen in wastewater by electrochemical coupling solid electrolyte |
| CN114956400B (en) * | 2022-06-01 | 2023-04-18 | 南京大学 | Device and method for recycling ammonia nitrogen in wastewater by electrochemical coupling solid electrolyte |
| CN115340166A (en) * | 2022-08-26 | 2022-11-15 | 中国科学院生态环境研究中心 | Flat-plate type membrane contact reactor and double-membrane wastewater deamination method |
| CN115340166B (en) * | 2022-08-26 | 2023-12-12 | 中国科学院生态环境研究中心 | Flat membrane contact reactor and double-membrane wastewater deamination method |
| EP4442354A1 (en) | 2023-04-05 | 2024-10-09 | Evonik Operations GmbH | Recovery of ammonia and sulfuric acid from ammonium sulfate-rich (waste) waters |
| EP4442355A1 (en) | 2023-04-05 | 2024-10-09 | Evonik Operations GmbH | Recovery of ammonia and sulfuric acid from ammonium sulfate-rich (waste) waters |
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Application publication date: 20120627 |