CN1219705C - Double-recovering circulation method for cyanic electroplating effluent and heavy metal-containing electroplating effluent - Google Patents
Double-recovering circulation method for cyanic electroplating effluent and heavy metal-containing electroplating effluent Download PDFInfo
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- CN1219705C CN1219705C CN 01131022 CN01131022A CN1219705C CN 1219705 C CN1219705 C CN 1219705C CN 01131022 CN01131022 CN 01131022 CN 01131022 A CN01131022 A CN 01131022A CN 1219705 C CN1219705 C CN 1219705C
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Abstract
The present invention relates to a double-recovery circulation method for cyanic electroplating waste water containing heavy metal, which mainly comprises: cyanic electroplating waste water passes through a recovery device made of ion exchange resin; noxious cyanide heavy metal matter is completely adsorbed at resin, and separated clean water is conveyed to the last making procedure to be used as washing water required by an electroplating making procedure; the noxious cyanide heavy metal matter is disengaged from the resin by a negative ion regenerant; the resin can be reused, and disengaged cyanide heavy metal matter is electrolyzed by an electropositive electrode and an electronegative electrode; cyanide is destroyed into nitrogen, carbon dioxide and clear water, wherein positive ion heavy metal matter is adsorbed at a negative electrode, and is recovered and reused. The present invention has the efficacy of pollution reduction, space saving and resource recovery and reutilization.
Description
Technical Field
The invention relates to amethod for double recovery and circulation of cyanogen and heavy metal-containing electroplating wastewater, which is to enable industrial wastewater containing cyanogen compounds and heavy metals to be processed into nontoxicity and completely recover and reuse heavy metal substances contained in the industrial wastewater, and a device for purifying water, recovering cyanogen compounds and heavy metal substances used in the whole process can be formed or recycled really, so that a double-circulation repeated recovery and use mode of water and a recovery device is formed, and the recovery method has low pollution, low cost, low material loss and high economic value.
Background
At present, due to social progress, modern people pay more and more attention to environmental protection, so that different treatment methods are developed and researched for various wastes with serious environmental pollution, so that the modern people can consider the environmental protection requirements in the process of industrial development. Although the current environmental protection treatment methods are many, all the methods have different defects. The analysis is carried out in the method for treating electroplating or other industrial wastewater containing cyanogen compounds or heavy metal substances, and the method can be divided into the following steps: chemical precipitation, ozone oxidation, biological treatment, cyanosis, and still pond methods, however, all have the following disadvantages:
FIG. 2 shows a chemical precipitation method, which uses chlorine and sodium hypochlorite bleaching powder as oxidants and addsThe treating method and process mainly include diluting electroplating waste water with clear water, and adding sodium hypochlorite (NaOCl, commonly called bleaching water) and liquid alkali (NaOH) to destroy Cyanogen (CN) in electroplating waste water-) Is non-toxic and produces nitrogen (N)2) Carbon dioxide (CO)2) And the like, and produce silver chloride (AgCl), copper chloride (CuCl) with toxicity2) The sludge containing metal compounds and water containing a small amount of heavy metal components, and finally the sludge containing cyanide, silver chloride, copper chloride and the like is solidified by a curing agent into blocks and can be buried underground. The main defects are as follows:
1. the required space is large: large-area sedimentation tanks are needed for sedimentation of the silver chloride sludge, so that large factory space is needed for treatment, and the cost of operators is increased unnecessarily.
2. Increase in processing time and energy costs: silver chloride and copper chloride sludge need to be solidified into blocks by using a curing agent, so that the treatment procedure is increased, and the energy cost (electric energy or fuel required for drying) is increased during treatment.
3. The problem of secondary pollution is easily generated: silver chloride and copper chloride are toxic heavy metal compounds, and need to be properly treated when buried, otherwise, underground water and soil are polluted, and secondary pollution is generated to harm the environment.
4. Waste of resources is formed: the water can not be recycled, and the heavy metal substances such as silver, copper and the like can not be recycled but buried, thereby undoubtedly forming the waste of resources. And the medicines consumed in the recovery process, such as sodium hypochlorite, are directly consumed in the whole process and cannot be recycled, so the treatment cost is extremely high, and the economic benefit is not met.
Another way of treating is ozone (O)3) An oxidation process having the formula:
the above method requires ozone, requires a special and expensive machine for generating ozone, is extremely expensive, and has a very limited effect because it can only perform the treatment operation for the cyanide compound and cannot recover other heavy metals.
The third method is the cyanosis method: the cyanide is capable of reacting with certain metal ions (Ni)+++Fe++) The method is characterized in that salt precipitation with low toxicity is formed, and in such a way, when a large amount of sludge is piled on the ground and is exposed to the sun, cyanide ions are easily decomposed from the sludge, and irreparable damage is caused.
The fourth method is a biological treatment method: the cyanogen ion is decomposed into acid by microbe, the concentration of cyanogen ion is lower than the poison degree, then it is discharged, the microbe needs to be acclimated to effectively exert its effect, the cost and time are very long, and when the microbe is added and discharged along with the discharged water, it is very easy to cause the ecological pollution of environment and unnecessary environmental destruction.
The fifth method is a pond standing method, that is, a method of oxidizing cyanide ions by wind exposure, which requires enlargement of the land and has a risk of polluting the groundwater.
From the above-mentioned various methods, the existing method for treating electroplating industrial wastewater has many disadvantages such as requiring large factory space, increasing treatment cost, easily causing secondary pollution problem, and forming resource waste, and needs to be improved.
Disclosure of Invention
The invention mainly aims to provide a method for double recovery and circulation of cyanogen and electroplating wastewater containing heavy metals, which overcomes the defects of the prior art and achieves the purposes of reducing pollution, saving space and recycling resources.
The purpose of the invention is realized as follows: a double recovery and circulation method of cyanogen and electroplating wastewater containing heavy metals comprises the following steps:
(1) the recovery device performs exchange: passing cyanide and electroplating wastewater containing heavy metal through a primary recovery device, wherein the device is an ionized exchange resin, after the wastewater discharged by the electroplating process passes through the recovery device, the cyanide heavy metal substances contained in the wastewater are completely absorbed in the resin and separated out clean water through resin exchange of the recovery device, and the separated clean water is sent to the previous procedure to be used as washing water in the electroplating process so as to achieve a first circulation type of water, while the exchange of the cyanide compound and the heavy metal substances in the recovery device is continuously carried out, and a sensor is used for detecting whether the adsorption of the resin reaches the saturation degree;
(2) treating with a regenerant: when the adsorption of the resin reaches saturation, adding a regenerant with anionic property, wherein cyanide metal substances in the state that the anionic cyanogen of the cyanide coats the heavy metal are separated from the resin, so that the resin is recovered to an unsaturated state and is further recycled, and generating liquid of the cyanide anion coating the heavy metal;
the method is characterized in that after the technical process is carried out, cyanide ions are destroyed: putting the liquid of heavy metal coated by cyanide anion into an electrolytic tank, and putting the liquid into the electrolytic tank at a positive electrode and a negative electrode with a voltage of 0.5-6V and a voltage of 0.01-6A/dm2Electrolyzing at 25-60 deg.C with current density to destroy cyanogen anion coated on heavy metal outer layer, so that toxic cyanogen can generate nitrogen gas and carbon dioxide as nontoxic gas, and heavy metal separated from cyanogen is adsorbed on negative electrode;
and (3) recovering heavy metals: stripping off the heavy metal from the negative electrode and recovering.
By the technical means, the invention can achieve the following effects:
1. through the exchange treatment of the resin, a large amount of clean water and a small amount of toxic substances can be separated immediately, so that the water can be treated only in a small space without the treatment in a large factory and a large space, and the burden of workers is reduced.
2. The double circulation can simultaneously enable the water purification and recovery device to be repeatedly used, the integral environmental protection effect is improved, the material use cost in the recovery process is improved, and a high-economic environmental protection treatment mode is formed.
3. The electrolysis treatment can rapidly and reliably treat toxic cyanogen into nontoxic gas (nitrogen and carbon dioxide) and recyclable metal without the trouble of poison and storage.
4. The design of the invention can not generate derivatives of heavy metal sludge such as silver chloride and the like, and the derivatives do not need to be processed, dried andsolidified into blocks, so that the processing cost is reduced, and the problem of secondary pollution caused by heavy metal burying can not be generated.
5. Because the heavy metal can be recycled, the heavy metal can be sold to save resources and reduce cost besides no environmental protection problem.
The following further description is made in conjunction with the accompanying drawings and preferred embodiments.
Drawings
FIG. 1 is a schematic view showing a process for treating an electroplating wastewater according to the present invention.
FIG. 2 is a schematic view showing a conventional process for treating an electroplating wastewater.
Detailed Description
Referring to FIG. 1, the method for treating electroplating wastewater according to the present invention comprises the following steps:
(1) the recovery device performs exchange: the cyanide electroplating wastewater is passed through a primary recovery device which is an ionized resin. After the waste water discharged by the electroplating process passes through the recovery device, cyanide and heavy metal substances contained in the waste water are completely adsorbed to the resin and clean water is separated out through resin exchange of the recovery device, the water can be sent to the previous procedure again at the moment and is used as washing water in the electroplating process so as to achieve a first circulation type of the water, the exchange of the cyanide compound and the heavy metal substances with the recovery device is continuously carried out, and a sensor is used for detecting whetherthe resin is saturated or not;
(2) treating with a regenerant: when the resin is saturated, adding an anion regenerant, and making the heavy metal substance of the cyanide be in a state that the heavy metal is coated by the cyanide anion through the characteristic that the cyanide of the cyanide is the anion, so that the cyanide metal substance can be separated from the resin, the resin is recovered to an unsaturated state and then recycled, and the liquid of the cyanide compound with the heavy metal is generated, so that the recycling device can be recycled, thereby forming the second cycle type of the invention, and the first cycle type of the purified water is a double-recycling double-cycle treatment method;
(3) destruction of cyanide ions: putting the heavy metal coated by the cyanide anions into an electrolytic bath, and then putting the heavy metal into the electrolytic bath by a positive electrode and a negative electrode with the voltage of 0.5-6V and the voltage of 0.01-6A/dm2Electrolyzing at 25-60 deg.C with current density to destroy cyanide anion coated on heavy metal outer layer and generate nitrogen (N)2) Carbon dioxide (CO)2) That is, toxic Cyanogen (CN) can be used-) Become non-toxic gas, and the metal can be separated from cyanogen and absorbed on negative electrode, so that it can be electrolyzed by electrolytic cellThe toxic cyanide and heavy metal liquid are decomposed into non-toxic water, nitrogen adsorbed to the positive electrode, carbon dioxide, and heavy metal adsorbed to the negative electrode.
(4) And (3) recovering: the metal is stripped from the negative electrode and recovered.
The above steps of the present invention, and the details and effects of the steps are further described as follows:
regarding the resin exchange:
the resin can make cyanide and heavy metal substances contained in the electroplating wastewater completely attached to the resin, and the cyanide and heavy metal substances are treated like filtering, so that clean water can be separated, and the clean water can be immediately recycled, therefore, the electroplating wastewater can be quickly separated into a large amount of water and a small amount of toxic cyanide heavy metal substances, and the water can be recycled, and the toxic cyanide heavy metal substances are convenient to be reprocessed due to small amount, and the problem of large space and large factory building treatment due to large volume is solved.
Regarding the regenerant treatment:
the invention detects the characteristic that cyanide is 'anion', therefore, the resin of saturated cyanide heavy metal treated with 'anion' regenerant can make the cyanide heavy metal substance separate from the resin through the interaction of anion, the saturated resin can return to the unsaturated state for exchanging again, and the cyanide heavy metal substance passes through the action of anion regenerant and is in the state that the cyanide anion coats the heavy metal, in other words, each heavy metal molecule (heavy metal is cation characteristic) is coated by the cyanide anion membrane, and can separate from the resin.
In addition, the method for monitoring whether the resin is saturated uses a sensor to sense the conductivity of the resin, when the conductivity reaches a set value, the resin is saturated, the exchange effect is reduced and needs to be replaced, so that the effect of monitoring the saturation accurately can be obtained.
Regarding the method for destroying cyanide ions:
the above-mentioned cyanide anion-coated cationThe cyanide anion of the liquid is destroyed by electrolysis via positive (positive) and negative (negative) electrodes to release heavy metal, and Cyanide (CN)-) Can be electrolyzed into nitrogen (N)2) Carbon dioxide (CO)2) Since nitrogen and carbon dioxide are non-toxic gases, they can be collected or emitted into the air, and the cationic heavy metals can be absorbed by the negative (negative) electrode of anion. Namely, the treatment of electrolytic destruction can generate nitrogen, carbon dioxide, clean water and heavy metal absorbed by the cathode, and the heavy metal can be separated from the electrode for recycling, so as to avoid wasting resources.
Claims (1)
1. A double recovery and circulation method of cyanogen and electroplating wastewater containing heavy metals comprises the following steps:
(1) the recovery device performs exchange: passing cyanide and electroplating wastewater containing heavy metal through a primary recovery device, wherein the device is an ionized exchange resin, after the wastewater discharged by the electroplating process passes through the recovery device, the cyanide heavy metal substances contained in the wastewater are completely absorbed in the resin and separated out clean water through resin exchange of the recovery device, and the separated clean water is sent to the previous procedure to be used as washing water in the electroplating process so as to achieve a first circulation type of water, while the exchange of the cyanide compound and the heavy metal substances in the recovery device is continuously carried out, and a sensor is used for detecting whether the adsorption of the resin reaches the saturation degree;
(2) treating with a regenerant: when the adsorption of the resin reaches saturation, adding a regenerant with anionic property, wherein cyanide metal substances in the state that the anionic cyanogen of the cyanide coats the heavy metal are separated from the resin, so that the resin is recovered to an unsaturated state and is further recycled, and generating liquid of the cyanide anion coating the heavy metal;
the method is characterized in that after the technical process is carried out, cyanide ions are destroyed: putting the liquid of heavy metal coated by cyanide anion into an electrolytic tank, and putting the liquid into the electrolytic tank at a positive electrode and a negative electrode with a voltage of 0.5-6V and a voltage of 0.01-6A/dm2Current densityElectrolyzing at 25-60 deg.C to destroy cyanogen anion coated on heavy metal outer layer, so that toxic cyanogen can generate nitrogen gas and carbon dioxide gas, and the heavy metal separated from cyanogen can be adsorbed on negative electrode;
and (3) recovering heavy metals: stripping off the heavy metal from the negative electrode and recovering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131022 CN1219705C (en) | 2001-09-03 | 2001-09-03 | Double-recovering circulation method for cyanic electroplating effluent and heavy metal-containing electroplating effluent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131022 CN1219705C (en) | 2001-09-03 | 2001-09-03 | Double-recovering circulation method for cyanic electroplating effluent and heavy metal-containing electroplating effluent |
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| CN1403385A CN1403385A (en) | 2003-03-19 |
| CN1219705C true CN1219705C (en) | 2005-09-21 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100577584C (en) * | 2006-07-10 | 2010-01-06 | 三达膜科技（厦门）有限公司 | Method for treating electroplating waste liquid containing heavy metals and recovering and reutilizing heavy metals |
| CN102531233B (en) * | 2011-12-21 | 2013-11-06 | 邵梦馨 | Heavy-metal-containing electroplating wastewater treatment and heavy metal recycling method |
| CN102583620B (en) * | 2012-02-16 | 2013-11-13 | 浙江工业大学 | Method for removing heavy metal ions from waste water and solidifying and recycling |
| CN103243348B (en) * | 2013-05-03 | 2014-09-17 | 广东新大禹环境工程有限公司 | Method and equipment for recovering heavy metal in electroplating wastewater |
| CN104418408A (en) * | 2013-08-30 | 2015-03-18 | 上海轻工业研究所有限公司 | Copper-electroplating wastewater treatment method and copper-electroplating wastewater treatment equipment |
| CN105366767B (en) * | 2015-12-10 | 2018-01-12 | 重庆青天环保材料有限公司 | The processing system and processing method of a kind of cyanide-containing electroplating water |
| CN108706790A (en) * | 2018-06-12 | 2018-10-26 | 杨柳 | A kind of device for automatic separation treatment of electroplating discharging liquid containing heavy metal |
| CN111377566A (en) * | 2018-12-27 | 2020-07-07 | 山东新海表面技术科技有限公司 | Method for surface treatment of cyanide in wastewater |
| CN114927658B (en) * | 2022-05-06 | 2024-02-27 | 中国科学院上海硅酸盐研究所 | Device and method for modifying surface of positive electrode material based on ion exchange membrane |
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