CN101353208A - Reclaiming process for electroplating cyanic waste water and equipment thereof - Google Patents
Reclaiming process for electroplating cyanic waste water and equipment thereof Download PDFInfo
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- CN101353208A CN101353208A CNA2007100092910A CN200710009291A CN101353208A CN 101353208 A CN101353208 A CN 101353208A CN A2007100092910 A CNA2007100092910 A CN A2007100092910A CN 200710009291 A CN200710009291 A CN 200710009291A CN 101353208 A CN101353208 A CN 101353208A
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Abstract
The invention discloses a process for reclaiming plating cyanide-containing wastewater, which comprises six steps that plating cyanide-containing wastewater is input to an ultrafilter for carrying out ultrafiltration separation by an ultrafiltration membrane so as to obtain dialysate, etc. In the invention, for the reason that plating cyanide-containing wastewater is treated by the steps of ultrafiltration, active carbon, reverse osmosis membrane, and the like, the process of the invention is combined process technology in which membrane separation is taken as the core, metal salt and water are separated, meanwhile concentrated solution with high concentration of metal and pure water or super pure water demanded by production are obtained. The noble metal-containing concentrated solution is supplied to the following extraction equipment for extracting metals, pure water or super pure water is used for production, noble metal reclamation and wastewater recycling are also realized.
Description
Technical field
The present invention relates to a kind of recoverying and utilizing method and device of electroplating wastewater, particularly relate to a kind of recovery technology and equipment thereof of electroplating cyanic waste water.
Background technology
The characteristic of electroplating cyanic waste water: mainly contain heavy metals such as prussiate and copper, silver, gold on the composition, copper, silver, gold and cyanogen complexing exist with forms such as Cu (CN) 2-, Ag (CN) 2-, Au (CN) 2-.The pH value is alkalescence, therefore in the normal state, and the difficult formation prussic acid gas (this gas severe toxicity) of prussiate.Usually the turbidity of water is low is that suspension content is low, contains the organism (being mainly electroplating additive) of trace in addition.The waste water that electroplating cyanic waste water mainly comes self-contained cyanogen electroplating process to produce wherein is mainly rinse water.Rinse water contain the metal of " copper, silver, gold " according to plating is corresponding, particularly " silver, gold " belongs to noble metal, has very high recovery value.The impurity of electroplating cyanic waste water is just few usually in addition, mainly be that to electroplate the rinse water adopted be pure water or ultrapure water owing to much contain cyanogen, and rinsing intensity is bigger, often the user drops into huge economy and the energy being pure water or ultrapure water with the tap water purifying, and after the production rinsing just with its discharging, hardly realizing that this water foreign matter content for tap water is very low, is a kind of very way of waste with this water discharging therefore, fully can be with it processing back reuse.
Summary of the invention
One object of the present invention is to provide a kind of recovery technology of electroplating cyanic waste water.Cost and water saving by the recyclable noble metal of this method, reduction tap water purifying.
Another object of the present invention is to provide a kind of equipment for reclaiming of electroplating cyanic waste water.
For achieving the above object, technical solution of the present invention is:
The present invention is a kind of recovery technology of electroplating cyanic waste water, and it may further comprise the steps: (1) is imported ultra-fine filter with electroplating cyanic waste water and is got dialyzate through the ultra-filtration membrane ultra-filtration and separation; (2) organism of this dialyzate input charcoal canister in charcoal absorption water; (3) dialyzate is held back all ions through the separation of reverse osmosis membrane separation system and is got film through liquid and concentrated solution, and concentrated solution carries out metal recovery; (4) film carries out the resin anion(R.A) exchange through liquid through the negative resin bed, and residual micro cyanide is exchanged from water; (5) film carries out resin cation exchange through liquid through positive resin bed, and the cationic exchange in the water is discharged H simultaneously
+, make PH=6-8 in the liquid; (6) film carries out the zwitterion exchange through liquid through mixing bed, gets high-purity water.
It is 1000-300000 that described ultra-filtration membrane gets the molecular weight cut-off scope.
The recovery system of electroplating cyanic waste water of the present invention, it comprises ultra-fine filter, charcoal canister, wastewater barrel, reverse osmosis membrane separation system, water purification jar, negative resin bed, positive resin bed and mixes bed; The inlet of described ultra-fine filter connects first water transfer pump, its outlet is communicated with charcoal canister, charcoal canister is communicated with wastewater barrel, the outlet of wastewater barrel connects second, third two water transfer pumps, wherein, the second water delivery pump outlet connects the metal recovery extraction element, and the 3rd water delivery pump outlet is communicated with the reverse osmosis membrane separation system, the outlet of described reverse osmosis membrane separation system is communicated with the water purification jar, and the outlet of water purification jar connects negative resin bed, positive resin bed successively and mixes bed.
Between the described ultra-fine filter and first water transfer pump, be communicated with micro-strainer.
Between the 3rd water transfer pump and reverse osmosis membrane separation system, be communicated with security personnel's strainer and high-pressure pump.
Between described water purification jar and negative resin bed, be communicated with the 4th water transfer pump.
Equipment of the present invention also comprises a tubulation water cooler, and this tubulation water cooler is connected with the input channel of wastewater barrel input channel, reverse osmosis membrane separation system, negative resin bed.
After adopting such scheme, since the present invention with electroplating cyanic waste water through step process such as ultrafiltration, gac, reverse osmosis membranes, be to be the COMBINED PROCESS of core with the membrane sepn, with metal-salt and water sepn, obtain the higher concentrated solution of containing metal concentration simultaneously and produce pure water or the ultrapure water that needs.Contain the noble metal concentrated solution and carry out the extraction of silver for follow-up desilver equipment, pure water or ultrapure water are back to product, and then the recycle of the waste water of the recovery of realization noble metal.
Cyanide-containing electroplating water is reclaimed economic worth with the following aspects:
A, can reclaim noble metal, particularly gold and silver;
B, can reuse water, conserve water resource, even save the cost of tap water purifying;
C, saved the input that traditional discharged wastewater met the national standard is handled;
D, have the protection environment far reaching significance.
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the structure iron of present device;
Fig. 3 is four kinds of common membrane sepn processes of the present invention.
Embodiment
1, equipment
As shown in Figure 2, the present invention is a kind of recovery system of electroplating cyanic waste water, and it comprises first water transfer pump 1, micro-strainer 2, ultra-fine filter 3, charcoal canister 4, wastewater barrel 5, second water transfer pump 6, the 3rd water transfer pump 7, security personnel's strainer 8, high-pressure pump 9, reverse osmosis membrane separation system 10, tubulation water cooler 20, water purification jar 30, the 4th water transfer pump 40, negative resin bed 50, positive resin bed 60, mixes bed 70 and Controlling System 80.
The inlet of described ultra-fine filter 3 connects first water transfer pump 1 through micro-strainer 2, and ultra-fine filter 3 outlets are communicated with charcoal canister 4; Charcoal canister 4 is communicated with wastewater barrel 5, the outlet of wastewater barrel 5 connects second, third two water transfer pumps 6,7, wherein, the outlet of second water transfer pump 6 connects metal recovery extraction element (not shown), and the outlet of the 3rd water transfer pump 7 is communicated with reverse osmosis membrane separation system 10 through security personnel's strainer 8, high-pressure pump 9; The outlet of described reverse osmosis membrane separation system 10 is communicated with water purification jar 30; The outlet of water purification jar 30 connects negative resin bed 50, positive resin bed 60 successively and mixes bed 70.The input channel of described tubulation water cooler 20 and wastewater barrel 5 input channels, reverse osmosis membrane separation system 10, negative resin bed 50 mutually, the 4th water transfer pump 40 inlets are connected.
Described Controlling System 80 is electrically connected electrical parts such as magnetic valve, resistivity meter F, water transfer pump, the action of control magnetic valve, resistivity meter F, water transfer pump etc.
The workflow of this equipment is: electroplating cyanic waste water pumps into micro-strainer 2 by first water transfer pump 1, flows in the wastewater barrel 5 via ultra-fine filter 3, charcoal canister 4 again; Concentrated solution in the wastewater barrel 5 carries out metal recovery through desilver equipment, film sees through liquid and pumps into security personnel's strainer 8 through second water transfer pump 6, the 3rd water transfer pump 7, pump into through high-pressure pump 9 again and enter water purification jar 30 after 10 separation of reverse osmosis membrane separation system are held back, the 4th water transfer pump 40 that is connected 30 outlets of water purification jar pumps into liquid negative resin bed 50, positive resin bed 60, mixes bed 70, generates ultra-pure water output at last.
2, method
The present invention is a kind of recovery technology (as shown in Figure 1) of electroplating cyanic waste water, and it may further comprise the steps: (1) is imported ultra-fine filter with electroplating cyanic waste water and is got dialyzate through the ultra-filtration membrane ultra-filtration and separation, and it is 1000-300000 that ultra-filtration membrane gets the molecular weight cut-off scope; (2) organism of this dialyzate input charcoal canister in charcoal absorption water; (3) dialyzate is held back all ions through the separation of reverse osmosis membrane separation system and is got film through liquid and concentrated solution, and concentrated solution carries out metal recovery; (4) film carries out the resin anion(R.A) exchange through liquid through the negative resin bed, and residual micro cyanide is exchanged from water; (5) film carries out resin cation exchange through liquid through positive resin bed, and the cationic exchange in the water is discharged H simultaneously
+, make PH=6-8 in the liquid; (6) film carries out the zwitterion exchange through liquid through mixing bed, gets high-purity water.
Principle of work of the present invention:
(1) " ultrafiltration-gac " pre-treatment
Electroplating wastewater contains a certain amount of organism, colloid, suspended solids etc., need tackle removal to it, the one, can prevent the obstruction of reverse osmosis membrane, prolong the cleaning interval, the 2nd, the organic content of electroplating in the water in the reuse water requirement water can not be too high, otherwise easily cause the electroplating quality problem.
Present technique adopts the pre-treatment as the film system such as " ultrafiltration, gac " combination treatment organism, colloid, suspended solids, the characteristic of holding back of ultra-filtration membrane is so that the organic molecular weight cut-off of standard is characterized, usually the molecular weight cut-off scope is at 1000-300000, ultra-filtration membrane can be with the larger molecular organics in the electroplating wastewater, colloid, suspended solids etc., gac is a kind of porous material, has very big specific surface area, effectively the organism in the planar water.The preprocessing part of this technology has novelty, and in a lot of engineering of water treatment, ultrafiltration places gac before the ultrafiltration usually with the combination of gac, and very technology then places ultrafiltration before the gac.The organism in the water can be better removed in this combination, and the longer service life of gac.
The process of the pure physics of this process: ultra-filtration membrane is with the larger molecular organics in the waste water (go in the waste water grease etc.) interception, and other material can not be blocked, waste water can or not change (promptly the pH of Jin Chukouing is identical) by pH by ultra-filtration membrane, and the pH of cyanide wastewater is between 8～10 usually.The temperature that ultrafiltration is imported and exported can not change substantially, and its temperature is at room temperature (20 ℃～30 ℃).
(2) reverse osmosis membrane separation system
Reverse osmosis membrane is the selectivity barrier between the two-phase.Generally, it is a kind of macromolecular material, feed liquid is carried out a kind of film of selective separation by the interaction energy of pressure reduction.The sepn process of being undertaken by it is called membrane sepn.It is that with the different of conventional filter film can separate in molecular range, and this process is a kind of physical process, the variation of phase need not take place and add auxiliary agent.Fig. 3 is four kinds of common membrane sepn processes.
Holding back liking all ions of reverse osmosis only allows water see through film, and water outlet is a deionized water.Reverse osmosis method can be removed soluble metal salt, organism, bacterium, colloidal particle, pyrogen, also can hold back all ions etc.
Prussiate in the waste water also belongs to the solvability salt, and reverse osmosis membrane can be tackled it, but because the dissociation degree of prussiate is lower, thus film to its interception rate unlike common salts substances height.So still have a certain amount of prussiate to see through film.
The process of the pure physics of this process: waste water sees through reverse osmosis membrane, organism in its water, inorganic salt (as the compound of silver, prussiate etc.) overwhelming majority is blocked, the liquid that sees through of film is primary pure water, and the higher waste water (being that waste water is concentrated) of concentrated solution metal-containing salt, the pH that the water inlet of film system, film see through liquid and membrane concentration liquid is suitable, all is alkalescence (pH is between 8～10).Waste water rises by dense water temp after the film system, and rising situation and cycles of concentration have relation.Therefore need lower the temperature to it, cooling just has heat exchanger to cool off, and water coolant adopts the liquid that sees through of film system, is lower than concentrated solution because see through the temperature of liquid.
(3) resin anion(R.A) exchange
Ion-exchange is divided into cationic exchange and anionresin, and this process using OH type anionite-exchange resin can discharge OH simultaneously with the anionresin in the water
-, the cryanide ion that contains of prussiate all is negatively charged ion such as CN
-, Ag (CN)
- 2, Cu (CN)
- 2, so its can from water, be exchanged by anionite-exchange resin.This process is a chemical process, and its reaction is as follows:
R-OH+CN-＞R-CN+OH
-
Illustrate:
A, R-OH represent anionite-exchange resin;
Above-mentioned reaction takes place and removes from water in B, all negatively charged ion.
By reverse osmosis membrane and anionresin combination, realized the decyanation of desalination and nearly 100%.
(4) resin cation exchange
H type Zeo-karb can discharge H simultaneously with the cationic exchange in the water
+, " the moon+sun " ion-exchange that itself and preposition anion exchange bed are formed has the function of desalination.Because electroplating cyanic waste water pH is an alkalescence, change not quite through its pH behind the membrane sepn, in addition after anion exchange bed, its pH further rises, therefore still being alkalescence, is neutral water but reuse water needs pH, and the cation exchange bed of this technology can be adjusted to neutrality with it.Therefore cation exchange bed has the function of two aspects: the one, regulate pH, and the 2nd, form desalination system with cloudy bed.This process is a chemical process, and its reaction is as follows:
R-H+Na
+-＞R-Na+H
+
Illustrate:
A, R-H represent Zeo-karb;
Above-mentioned reaction takes place and removes from water in B, all positively charged ions.
(5) mixed bed ion exchange
Mixed bed is a zwitterion mixed with resin ion exchange bed together, because closely alternately contact of yin, yang resin in the mixed bed.As many sun beds and cloudy bed series connection being arranged together, constitute countless miniature multiple beds, carry out repeatedly desalination repeatedly, thereby water outlet purity height.
R-H+Na
+-＞R-Na+H
+
R-OH+Cl
--＞R-Cl+OH
-
H
++OH
--＞H
2O
Illustrate:
A, R-H represent Zeo-karb;
B, all positively charged ion and Na
+The same reaction of anti-generation;
C, all negatively charged ion and Cl
-The same reaction of anti-generation.
Claims (7)
1, a kind of recovery technology of electroplating cyanic waste water, it is characterized in that: it may further comprise the steps: (1) is imported ultra-fine filter with electroplating cyanic waste water and is got dialyzate through the ultra-filtration membrane ultra-filtration and separation; (2) organism of this dialyzate input charcoal canister in charcoal absorption water; (3) dialyzate is held back all ions through the separation of reverse osmosis membrane separation system and is got film through liquid and concentrated solution, and concentrated solution carries out metal recovery; (4) film carries out the resin anion(R.A) exchange through liquid through the negative resin bed, and residual micro cyanide is exchanged from water; (5) film carries out resin cation exchange through liquid through positive resin bed, and the cationic exchange in the water is discharged H simultaneously
+, make PH=6-8 in the liquid; (6) film carries out the zwitterion exchange through liquid through mixing bed, gets high-purity water.
2, the recovery technology of electroplating cyanic waste water according to claim 1 is characterized in that: it is 1000-300000 that described ultra-filtration membrane gets the molecular weight cut-off scope.
3, a kind of recovery system of recovery technological design of electroplating cyanic waste water according to claim 1 is characterized in that: it comprises ultra-fine filter, charcoal canister, wastewater barrel, reverse osmosis membrane separation system, water purification jar, negative resin bed, positive resin bed and mixes bed; The inlet of described ultra-fine filter connects first water transfer pump, its outlet is communicated with charcoal canister, charcoal canister is communicated with wastewater barrel, the outlet of wastewater barrel connects second, third two water transfer pumps, wherein, the second water delivery pump outlet connects the metal recovery extraction element, and the 3rd water delivery pump outlet is communicated with the reverse osmosis membrane separation system, the outlet of described reverse osmosis membrane separation system is communicated with the water purification jar, and the outlet of water purification jar connects negative resin bed, positive resin bed successively and mixes bed.
4, the recovery system of electroplating cyanic waste water according to claim 3 is characterized in that: be communicated with micro-strainer between the described ultra-fine filter and first water transfer pump.
5, the recovery system of electroplating cyanic waste water according to claim 3 is characterized in that: be communicated with security personnel's strainer and high-pressure pump between the 3rd water transfer pump and reverse osmosis membrane separation system.
6, the recovery system of electroplating cyanic waste water according to claim 3 is characterized in that: be communicated with the 4th water transfer pump between described water purification jar and negative resin bed.
7, the recovery system of electroplating cyanic waste water according to claim 3 is characterized in that: it also comprises a tubulation water cooler, and this tubulation water cooler is connected with the input channel of wastewater barrel input channel, reverse osmosis membrane separation system, negative resin bed.
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|---|---|---|---|
| CN2007100092910A CN101353208B (en) | 2007-07-26 | 2007-07-26 | Reclaiming process for electroplating cyanic waste water and equipment thereof |
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|---|---|---|---|
| CN2007100092910A CN101353208B (en) | 2007-07-26 | 2007-07-26 | Reclaiming process for electroplating cyanic waste water and equipment thereof |
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| CN101353208B CN101353208B (en) | 2010-09-29 |
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| CN105712517A (en) * | 2016-04-11 | 2016-06-29 | 浙江碧源环保科技有限公司 | Copper-containing electroplating rinse wastewater treatment system and treatment process |
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| US3656893A (en) * | 1970-07-02 | 1972-04-18 | Du Pont | Ion exchange removal of cyanide values |
| CN1282616C (en) * | 2004-12-04 | 2006-11-01 | 海宁市海整整流器有限公司 | Recovering and using technology of water in electroplating |
| CN1323957C (en) * | 2005-10-17 | 2007-07-04 | 海宁市海整整流器有限公司 | Electrosilvering cleaning water comprehensive utilization |
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2007
- 2007-07-26 CN CN2007100092910A patent/CN101353208B/en not_active Expired - Fee Related
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| CN102452703A (en) * | 2010-10-27 | 2012-05-16 | 王辉 | Method for recovering resources from gold mine cyanide barren solution |
| CN102071727A (en) * | 2010-12-23 | 2011-05-25 | 浙江精功新能源有限公司 | Reuse technology for photovoltaic ultrapure water wastewater and dual-pipeline water supply device |
| CN102071727B (en) * | 2010-12-23 | 2012-12-12 | 浙江精功新能源有限公司 | Reuse technology for photovoltaic ultrapure water wastewater and dual-pipeline water supply device |
| CN102358643A (en) * | 2011-06-21 | 2012-02-22 | 长春一汽富维高新汽车饰件有限公司 | Apparatus for recovering and reusing electroplating rinse water, and method thereof |
| CN102424487A (en) * | 2011-10-27 | 2012-04-25 | 四维尔丸井(广州)汽车零部件有限公司 | Electroplating wastewater recycling water quality improvement process |
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| CN103011452B (en) * | 2012-12-07 | 2014-05-28 | 上海瑞勇实业有限公司 | High efficiency ion exchange electroplating wastewater reuse treatment system |
| CN103011452A (en) * | 2012-12-07 | 2013-04-03 | 上海瑞勇实业有限公司 | High efficiency ion exchange electroplating wastewater reuse treatment system |
| CN104030480A (en) * | 2013-03-07 | 2014-09-10 | 昆山苏杭电路板有限公司 | Treatment method for cyanogen-containing rinsing wastewater |
| CN106745944A (en) * | 2015-11-24 | 2017-05-31 | 湖南衡阳新澧化工有限公司 | A kind of electroplating sewerage processes all-in-one |
| CN105712517A (en) * | 2016-04-11 | 2016-06-29 | 浙江碧源环保科技有限公司 | Copper-containing electroplating rinse wastewater treatment system and treatment process |
| CN108147580A (en) * | 2017-12-18 | 2018-06-12 | 五邑大学 | A kind of nickeliferous wire board plating wastewater processing system of cupric and method |
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| CN109650636A (en) * | 2018-12-26 | 2019-04-19 | 国电新能源技术研究院有限公司 | A kind of brine waste processing system |
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