CN103086558A - Treatment method of copper chloride hydroxide production wastewater - Google Patents
Treatment method of copper chloride hydroxide production wastewater Download PDFInfo
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- CN103086558A CN103086558A CN2013100527640A CN201310052764A CN103086558A CN 103086558 A CN103086558 A CN 103086558A CN 2013100527640 A CN2013100527640 A CN 2013100527640A CN 201310052764 A CN201310052764 A CN 201310052764A CN 103086558 A CN103086558 A CN 103086558A
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- wastewater
- waste water
- copper chloride
- factory effluent
- ion exchange
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Abstract
The invention relates to a treatment method of copper chloride hydroxide production wastewater. The treatment method comprises the following steps: carrying out solid-liquid separation treatment on production wastewater so as to obtain a first liquid supernatant, adding ammonia water into the first liquid supernatant so as to form a mixing system, and adjusting the pH value of the mixing system to be 4.5-5.5; oxidizing the mixing system so as to completely convert cuprous ions into copper ions, thereby obtaining first wastewater; feeding the first wastewater into an ion exchange system to remove free copper ions through adsorption, thereby obtaining second wastewater, wherein the ion exchange system comprises a plurality of reaction columns which are connected in series and filled with active resins, and the flow rate of the first wastewater in the reaction column is controlled to be 8-10m3/h; feeding the second wastewater into an evaporation system to evaporate, thereby obtaining a concentrated solution, and then carrying out cooling, crystallizing, and solid-liquid separation treatment on the concentrated solution so as to obtain ammonium chloride. According to the treatment method, the recovery rate of resources in production wastewater is effectively improved, and the production efficiency also can be improved; and meanwhile, the method is environment-friendly, and has a good application prospect.
Description
Technical field
The present invention relates to field of waste water treatment, especially a kind of method that copper in the basic copper chloride factory effluent, nitrogen element are processed.
Background technology
The nitrogen element is the indispensable nutritive element of plant, if but enter water body, particularly flow lake, bay more slowly, easily cause algae and other microorganism amount reproductions in water, form eutrophication pollution, a large amount of dissolved oxygens that consume in water worsen water ecological setting, cause " the eutrophication phenomenon " of water body.
The main component of basic copper chloride (BCC) factory effluent is ammonium chloride and a small amount of cupric ion, ammonium sulfate, sodium-chlor, the intractability of this kind waste water embodies a concentrated reflection of the removal problem of ammonia nitrogen in waste water, and has increased its intractability because wherein containing all the other impurity such as heavy metal copper.
Existing treatment process to this type of waste water mainly contains: ion exchange method, membrane separation process, electrolytic process, method of evaporation etc.But existing treatment process lacks the recycling to cuprous ion, makes the part copper-containing compound flow into environment, not only wastes resource, also can be to environment; In addition, prior art is not high for the processing efficiency of ammonia nitrogen, in the urgent need to a kind for the treatment of process of more efficient, high-environmental,
Summary of the invention
For addressing the above problem, the invention provides a kind for the treatment of process of basic copper chloride factory effluent, comprise the steps:
Step I: described factory effluent is carried out solid-liquid separation process acquisition the first supernatant liquor, think to add in described the first supernatant liquor ammoniacal liquor to form mixed system, regulating the pH value is 4.5～5.5;
Step II: described mixed system is carried out oxidation, make cuprous ion be converted into cupric ion fully, obtain the first waste water;
Step II I: change described the first waste water over to ion exchange system absorption and remove the free copper ion, obtain the second waste water; Wherein, described ion exchange system comprises the many reaction columns that are filled with the series connection of reactive resin, and controlling the flow of the first waste water in described reaction column is 8～10m
3/ h;
Step IV: change described the second waste water over to vapo(u)rization system and evaporate the acquisition concentrated solution, concentrated solution obtains ammonium chloride through crystallisation by cooling after solid-liquid separation is processed.
Wherein, described Step II is to make described mixed system carry out oxidation by efflux aerator and air blast tower, and control jet aerating apparatus aeration rate is 280m
3The flow of/h, mixed system is 10m
3/ h.
Wherein, described vapo(u)rization system is the MVR vaporizer.
Wherein, the filtrate that obtains after in described step IV, solid-liquid separation is processed utilizes the break point chlorination method to remove ammonia nitrogen.
Wherein, the described ion exchange system reactive resin of filling is macropore chelating resin or macropore strong acid resin.
Beneficial effect: basic copper chloride production wastewater treatment method provided by the invention, can effectively remove the cupric ion of various valence states in waste water, improve resource recycling efficient; On the other hand, the present invention has improved the removal method of ammonia nitrogen, adopts single MVR vaporizer, can not only save the energy, reduces costs, and can greatly improve the organic efficiency of ammonia nitrogen.The present invention effectively improves the resource recycling rate by the improvement to method of wastewater treatment, can improve productivity effect again, and is simultaneously environmentally friendly, has a good application prospect.
Description of drawings
Fig. 1 is the process flow sheet of basic copper chloride production wastewater treatment method of the present invention.
Embodiment
Below, in connection with specific embodiment, the present invention is elaborated.
The main component of basic copper chloride (BCC) factory effluent is ammonium chloride and a certain amount of cupric ion (Cu
2+), cuprous ion (Cu
+), ammonium sulfate, sodium-chlor, removal problem and cupric ion that the intractability of waste water embodies a concentrated reflection of ammonia nitrogen reclaim problem.
This treatment process for the basic copper chloride factory effluent provided by the invention can improve the cupric ion organic efficiency of various valence states, further makes the copper resource obtain recycle; Also greatly improve the processing efficiency of ammonia nitrogen, produced efficient economic benefit.
As shown in Figure 1, this treatment process for the basic copper chloride factory effluent comprises the steps:
Step I: described BCC factory effluent is carried out solid-liquid separation process acquisition the first supernatant liquor, add ammoniacal liquor to form mixed system in described the first supernatant liquor, regulating the pH value is 4.5～5.5.
At first, BCC factory effluent and Cleaning Wastewater transfer are entered settling tank, precipitate slightly large particle and a small amount of suspended substance.The heavy mud that obtains after precipitation is transferred to the workshop reuse.Contain relatively large copper-containing compound in heavy mud, copper-containing compound can be back to Workshop Production, produce economic benefit when reducing the wastewater treatment difficulty.
The first supernatant liquor that obtains after precipitation enters storage pool 1, reaches until the first supernatant liquor to be transferred to purification pot after a certain amount of.Install pipeline between storage pool 1 and purification pot has automatic medicine adding apparatus, is used for adding ammoniacal liquor to form mixed system toward the first supernatant liquor.Include the pH probe that contacts with reaction solution in this automatic medicine adding apparatus, the pH value of energy on-line monitoring the first supernatant liquor.According to the monitor value of pH probe, automatic medicine adding apparatus repeatedly adds ammoniacal liquor easily in batches in pipeline, regulates 4.5～5.5 scopes that are stabilized in of mixed system pH value.The use of ammoniacal liquor automatic medicine adding apparatus has improved mechanical automation, has reduced manually-operated error; And the technique that the ammoniacal liquor classification adds makes copper sedimentation wherein more complete, and adding of ammoniacal liquor makes system generate NH
3H
2O-NH
4The Cl buffering system is beneficial to the pH that controls mixed system and changes.
Step II: be transferred to storage pool 2 through the reacted mixed system of purification pot, again add ammoniacal liquor to make pH be stabilized in 6～7 this moment.Adopt efflux aerator, mixed system is carried out aeration, the control aeration rate is 280m
3The flow of/h, mixed system is 10m
3/ h.This step is used for replacing existing whipping appts, and is with low cost, can not only promote that ammoniacal liquor mixes, and balanced solution pH can also and promote Cu
+Conversion.
Controlling the mixed system flow is 10m
3/ h changes above-mentioned mixed system over to the air blast tower, blasts the oxidation that air carries out the degree of depth, makes Cu wherein
+Be oxidized to Cu fully
2+, prevent from discharging water quality Cu
+Residual.On the other hand, owing to adding the mixed system after ammoniacal liquor that intensification is reached 60～70 ℃, be unfavorable for subsequent disposal, so the air blast tower blasts large quantity of air and can lower the temperature to mixed system simultaneously, effectively prevent the poisoning of resin in follow-up ion-exchange step.The method of sampling Detection be can adopt in this step, namely when the temperature of mixed system is down to below 50 ℃, strong acid or strong oxidizer added in the mixed system sample that extracts, and α-benzoinoxime etc., through colour contrast judgement Cu
+Whether be converted into Cu fully
2+Obtain the first waste water after completing steps II.
Step II I: above-mentioned the first waste water is pumped into ion exchange system, in order to adsorb wherein remaining cupric ion.The present embodiment ion exchange system adopts the reaction column of 3～4 series connection, and wherein filling reactive resin is to adopt macropore chelating resin or macropore strong acid resin, and the flow of controlling the first waste water process ion exchange system is 8～10m
3/ h.The first waste water quality heavy metal content after processing through ion exchange system can reach discharging standards.Wherein, resin absorption is saturated goes out cupric chloride by resolving hydrochloric acid, available ammoniacal liquor regeneration, and resin can reuse.The cupric chloride that parses can be back to Workshop Production; Resin can reuse at the residual alkali of residual acid of resolving, collect in regenerative process on the other hand, reduces acid consumption alkaline consumption.The ion exchange system water outlet forms the second waste water and enters and purify the mother liquor pond.
Step IV: change described the second waste water over to vapo(u)rization system and evaporate acquisition concentrated solution and remaining liquid, the concentrated solution crystallisation by cooling obtains ammonium chloride.
The second waste water in purification mother liquor pond contains a large amount of ammonia nitrogens, if be discharged into environment like this, can cause great environmental pollution, and is unfavorable for the resource recycling, reduces costs, and the second waste water need to be pumped into vapo(u)rization system and carry out evaporation concentration, reclaims ammonia nitrogen.The vapo(u)rization system of the present embodiment is to adopt MVR vaporizer (mechanical vapor recompression), it is the energy that re-uses the secondary steam that it self produces, vapour compressor recompresses rear re-using to regeneration steam, thereby reduces a technology of the demand of the energy to external world.The present embodiment greatly reduces energy consumption than existing multiple-effect evaporation technique, has saved processing cost.Obtain concentrated solution and remaining liquid after processing through the MVR vaporizer, wherein, concentrated solution is through overcooling, crystallization, then suction filtration, centrifugal treating can obtain ammonium chloride product.Filtrate after suction filtration, centrifugal treating all adopts the break point chlorination method to transfer to above-mentioned vapo(u)rization system degree of depth removal ammonia nitrogen wherein.Distilled water after evaporation reaches emission standard, enters circulating water pool, can recycle after cooling.
Grope through test of many times, multi-effect evaporation system adopts independent MVR evaporation, uses electric energy to replace steam, to energy-saving and emission-reduction, reduce costs of great advantage.
Adopt above-mentioned steps to process the BCC factory effluent of four batches, after testing: the various pollutents such as copper, ammonia nitrogen have all obtained comparatively effectively removing, and the pH value also reaches emission request, and operation result is as shown in table 1:
The every detected result of table 1BCC factory effluent
From above data, the every pollutent parameter of waste water in discharge water after treatment all reaches the requirement of wastewater discharge standard, realizes qualified discharge, also reached the design requirements of expection simultaneously.
Claims (5)
1. the treatment process of a basic copper chloride factory effluent, is characterized in that, comprises the steps:
Step I: described factory effluent is carried out solid-liquid separation process acquisition the first supernatant liquor, add ammoniacal liquor to form mixed system in described the first supernatant liquor, regulating the pH value is 4.5～5.5;
Step II: described mixed system is carried out oxidation, make cuprous ion be converted into cupric ion fully, obtain the first waste water;
Step II I: change described the first waste water over to ion exchange system absorption and remove the free copper ion, obtain the second waste water; Wherein, described ion exchange system comprises the many reaction columns that are filled with the series connection of reactive resin, and controlling the flow of the first waste water in described reaction column is 8～10m
3/ h;
Step IV: change described the second waste water over to vapo(u)rization system and evaporate the acquisition concentrated solution, concentrated solution obtains ammonium chloride through crystallisation by cooling after solid-liquid separation is processed.
2. the treatment process of basic copper chloride factory effluent according to claim 1, is characterized in that, wherein, described Step II is to make described mixed system carry out oxidation by efflux aerator and air blast tower, and controlling described efflux aerator aeration rate is 280m
3The flow of/h, described mixed system is 10m
3/ h.
3. the treatment process of basic copper chloride factory effluent according to claim 1, is characterized in that, described vapo(u)rization system is the MVR vaporizer.
4. the treatment process of basic copper chloride factory effluent according to claim 1, is characterized in that, the filtrate that obtains after in described step IV, solid-liquid separation is processed utilizes the break point chlorination method to remove ammonia nitrogen.
5. the treatment process of basic copper chloride factory effluent according to claim 1, is characterized in that, the reactive resin that described ion exchange system is filled is macropore chelating resin or macropore strong acid resin.
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| CN2013100527640A CN103086558A (en) | 2013-02-18 | 2013-02-18 | Treatment method of copper chloride hydroxide production wastewater |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449501A (en) * | 2013-09-01 | 2013-12-18 | 深圳市危险废物处理站有限公司 | Comprehensive utilization method of waste liquor in production of basic cupric carbonate |
| CN105753235A (en) * | 2016-03-07 | 2016-07-13 | 吴江梅堰三友染料化工有限公司 | 3, 3', 4, 4'-tetraaminobiphenyl wastewater comprehensive treatment and resource utilization method |
| CN111517546A (en) * | 2020-04-07 | 2020-08-11 | 江苏南大华兴环保科技股份公司 | Treatment method for recycling magnesium salt in copper-containing wastewater |
| CN112194305A (en) * | 2020-09-30 | 2021-01-08 | 南京绿岛环境工程有限公司 | Hydrazine hydrate wastewater treatment process |
| CN113546446A (en) * | 2021-07-28 | 2021-10-26 | 江西东江环保技术有限公司 | Method for recovering copper in BCC synthetic mother liquor by using cationic resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865166A (en) * | 2005-05-18 | 2006-11-22 | 陈晶 | Microwave circulating disposal process for printed plate board etching waste liquor |
| CN101391799A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for recovery processing of ammonia nitrogen from printed circuit board waste liquid |
| CN102320703A (en) * | 2011-06-02 | 2012-01-18 | 广州科城环保科技有限公司 | A kind of etching waste liquor is produced the recovery method of the mother liquor behind the basic copper chloride |
-
2013
- 2013-02-18 CN CN2013100527640A patent/CN103086558A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865166A (en) * | 2005-05-18 | 2006-11-22 | 陈晶 | Microwave circulating disposal process for printed plate board etching waste liquor |
| CN101391799A (en) * | 2007-09-20 | 2009-03-25 | 深圳市东江环保股份有限公司 | Method for recovery processing of ammonia nitrogen from printed circuit board waste liquid |
| CN102320703A (en) * | 2011-06-02 | 2012-01-18 | 广州科城环保科技有限公司 | A kind of etching waste liquor is produced the recovery method of the mother liquor behind the basic copper chloride |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449501A (en) * | 2013-09-01 | 2013-12-18 | 深圳市危险废物处理站有限公司 | Comprehensive utilization method of waste liquor in production of basic cupric carbonate |
| CN103449501B (en) * | 2013-09-01 | 2015-11-18 | 深圳市危险废物处理站有限公司 | The method of comprehensive utilization of waste liquor in production of basic cupric carbonate |
| CN105753235A (en) * | 2016-03-07 | 2016-07-13 | 吴江梅堰三友染料化工有限公司 | 3, 3', 4, 4'-tetraaminobiphenyl wastewater comprehensive treatment and resource utilization method |
| CN111517546A (en) * | 2020-04-07 | 2020-08-11 | 江苏南大华兴环保科技股份公司 | Treatment method for recycling magnesium salt in copper-containing wastewater |
| CN111517546B (en) * | 2020-04-07 | 2022-03-01 | 江苏南大华兴环保科技股份公司 | Treatment method for recycling magnesium salt in copper-containing wastewater |
| CN112194305A (en) * | 2020-09-30 | 2021-01-08 | 南京绿岛环境工程有限公司 | Hydrazine hydrate wastewater treatment process |
| CN113546446A (en) * | 2021-07-28 | 2021-10-26 | 江西东江环保技术有限公司 | Method for recovering copper in BCC synthetic mother liquor by using cationic resin |
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Application publication date: 20130508 |