CN101875520A - Processing method of electroplating wastewater containing cyanogens and chrome - Google Patents
Processing method of electroplating wastewater containing cyanogens and chrome Download PDFInfo
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Abstract
The invention provides a processing method of electroplating wastewater containing cyanogens and chrome, comprising the following steps of: regulating the pH value of mixed electroplating wastewater containing cyanogens and chrome; introducing O3 into an oxidation pond; adding hydrazine hydrate into a reduction pond, and introducing the wastewater into a precipitator after reducing the wastewater; discharging 10-30 percent of clear solution reaching a standard after precipitation, and enabling 70-90 percent of clear solution to flow into a middle wastewater pond; regulating the pH value of the wastewater in the middle wastewater pond, and adding NaHSO3; introducing the wastewater in the middle wastewater pond into a medium filter and a precision filter; introducing the outlet water of the precision filter for first-segment nanofiltration processing; enabling the concentrated water in the first-segment nanofiltration to enter reverse osmosis-segment processing; enabling the concentrated water in the reverse osmosis segment to finally enter second-segment nanofiltration, and enabling the permeation liquid of the second-segment nanofiltration to return to the middle wastewater pond for circular processing; and enabling the permeation concentrated water of the second-segment nanofiltration to return to an original water tank for circular processing. The method can be used for processing the mixed electroplating wastewater containing cyanogen and chrome, other heavy metals and the like, and not only can realize higher recycle rate and lower the cost, but also can reduce energy consumption.
Description
Technical field
The present invention relates to the treatment process of electroplating wastewater containing cyanogens and chrome, belong to the technical field of electroplating wastewater processing.
Background technology
Cyanide electroplating and chromium plating are to use very general plating kind.Wherein cyanide electroplating has technical maturity, is easy to management, coating knot product are careful, color and luster is attractive in appearance, plurality of advantages such as covering power and dispersive ability are good, be most widely used electroplating technology. but produce a large amount of cyanide wastewater in the cyanide electroplating process, have carcinogenic, teratogenesis or mutagenic highly toxic substance, to human and environmental hazard is very big; Chromium plating produces contains also bigger to the environment structure threat of hexavalent chromium wastewater.If it is can carry out regeneration, significant for the Sustainable development of environment protection and electroplating industry to this class waste water.
Chinese patent CN100413791C discloses the integrated membrane sepn utilization process of a kind of electroplating wastewater, CN101481157A discloses a kind of process for advanced treatment of electroplating waste by integrated membrane, CN1590322A discloses a kind of membrane separating method of electroplating wastewater processing zero release, these methods are to handle at the rinse water of single plating kind, are unsuitable for containing the processing that cyanogen contains chromium mixing electroplating wastewater.
Chinese patent CN101234828A has announced a kind of integrated electroplating treatment method for waste water, particularly with cyclically utilizing after the electroplating wastewater processing of comprehensive discharge and reclaim the technology of noble metal resource.A key of this waste water treatment process is that chromate waste water and cyanide wastewater need to handle respectively earlier, and then combination treatment, and restricted application is not suitable for the chromate waste water of a lot of medium and small electroplating enterprises and the occasion that cyanide wastewater does not have independent gathering system.
Chinese patent CN101318732B discloses a kind of technology that reclaims electroplating waste to prepare pure water, the electroplating wastewater that contains heavy metal ion is used pure water through producing after pre-treatment, nanofiltration and the reverse osmosis isolation successively, though it is better that this technology is produced water water quality, but invest bigger, the energy consumption height is not announced the treatment process of dense water.
Summary of the invention
At the shortcoming of prior art, the technical problem to be solved in the present invention provides the treatment process of electroplating wastewater containing cyanogens and chrome, and this method can be handled and contain cyanogen and contain chromium and other heavy metal etc. and mix electroplating wastewater, and can realize higher reclamation rate and reduce energy consumption.
The technical scheme that the present invention solves its technical problem is: the treatment process of electroplating wastewater containing cyanogens and chrome is characterized in that comprising following processing step:
1) the pH value that cyanogen contains chromium mixing electroplating wastewater that contains in the broken cyanide pond is adjusted in 8.5 ~ 9.5;
2) start O
3Producer is pressed O
3: CN
-Mass ratio 4:1 ~ 6:1 feed O
3, to stir, the controlled oxidation time is to enter the reduction pond after 45 ~ 60 minutes;
3) press hydrazine hydrate (N
2H
2H
2O) being 0.75:1 ~ 1:1 with chromic mass ratio adds the reductive agent hydrazine hydrate in the reduction pond, stir, and waste water recovery time in the reduction pond is sent into settling vessel after being 30 ~ 60 minutes and carries out solid-liquid separation;
4) 10% ~ 30% qualified discharge of post precipitation clear liquid, 70% ~ 90% flows into middle wastewater disposal basin carries out subsequent disposal;
5) the pH value with waste water in the middle wastewater disposal basin is adjusted to 6 ~ 7, and adds NaHSO
3, controlled oxidation reduction potential 250 ~ 400mV;
6) utilize low-pressure pump that the waste water in the middle wastewater disposal basin is sent into medium filter and accurate filter, remove suspended substance and colloid, make pollution index SDI＜3;
7) water outlet of accurate filter is sent into 1 section nanofiltration processing with high-pressure pump, and the rate of recovery of 1 section nanofiltration is 40 ~ 60%, sees through liquid and is collected in the reuse water tank;
8) the dense water of 1 section nanofiltration enters the processing of reverse osmosis section by topping-up pump, and the rate of recovery is 40 ~ 60%, and reverse osmosis sees through liquid and is collected in the reuse water tank;
The dense water of 9) reverse osmosis section enters 2 sections nanofiltrations at last, and the liquid that sees through of 20 ~ 40%, 2 sections nanofiltrations of the rate of recovery of 2 sections nanofiltrations is back to the import of reverse osmosis section and carries out circular treatment;
10) with 2 sections saturating dense water of nanofiltration, account for 10% ~ 30% of the former water yield, return the raw water box circular treatment.
Wherein, the medium filter in the step 6) is any one in more medium filter (filtration medium is hard coal and quartz sand), fiber ball filter (filtration medium is a fibrous nodules), the fabric filter (filtration medium is a fiber).
1 section used nanofiltration membrane of nanofiltration is the bear nanofiltration membrane in the step 7), and molecular weight cut-off is 100 ~ 150; The requirement of its separation performance is: in NaCl concentration is 2000mg/L, and temperature is 25 ℃, and the operating pressure 0.48Mpa and the rate of recovery are under 15% the condition, the transmitance of NaCl＜5 ~ 15%.
The used reverse osmosis membrane of reverse osmosis is an anti-pollution reverse osmosis membrane in the step 8), and the requirement of its separation performance is: in NaCl concentration is 2000mg/L, and temperature is 25 ℃, and the operating pressure 1.0Mpa and the rate of recovery are under 15% the condition, the transmitance of NaCl＜1%.
2 sections used nanofiltration membrane of nanofiltration are the bear nanofiltration membrane in the step 9), and molecular weight cut-off is 300 ~ 600; The requirement of its separation performance is: at MgSO
4Concentration is 2000mg/L, and temperature is 25 ℃, and the operating pressure 0.48Mpa and the rate of recovery are under 15% the condition, MgSO
4Transmitance＜3%.
The treatment process of electroplating wastewater containing cyanogens and chrome of the present invention has following beneficial effect: (1) can be used for handling and contains cyanogen and contain chromium and other heavy metal etc. and mix electroplating wastewater, and can realize higher reclamation rate 70 ~ 90%, reaches as high as 90%; (2) 2 sections dense water of nanofiltration finally return the wastewater disposal basin circular treatment, and, both simplified dense water technology from medium filter discharging part processing waste water up to standard, solved the accumulation problem of salinity in system again, guarantee the stability of nanofiltration reverse osmosis operation, also reduced processing cost; (3) appropriate design by nanofiltration and reverse osmosis, make that the liquid that sees through that sees through liquid and reverse osmosis of 1 section nanofiltration all can direct reuse, the required working pressure of reverse osmosis has made full use of the overbottom pressure of 1 section dense water of nanofiltration, make that topping-up pump power is less, and 2 sections nanofiltrations utilize the overbottom pressure of reverse osmosis concentrated water fully, need not set up water pump, have than obvious energy-saving effect.
Description of drawings
Fig. 1 is the technological process of the treatment process of electroplating wastewater containing cyanogens and chrome of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
Embodiment 1
A kind of cyanogen that contains contains chromium mixing electroplating wastewater, and the pH value is 7.5, and wherein total cyanide content is 21.8mg/L, and content of 6-valence Cr ions is 27.5mg/L, and total heavy metal ion content such as copper, zinc is less than 100mg/L.Adopt method as shown in Figure 1:
(1) the pH value of electroplating wastewater is adjusted to 8.5 with 20% NaOH solution;
(2) start O
3Producer is pressed O
3: CN
-Mass ratio be that 4:1 feeds O
3, to stir, the controlled oxidation time is to enter the reduction pond in 45 minutes after (min);
(3) press hydrazine hydrate (N
2H
2H
2O) being 0.75:1 with chromic mass ratio adds the reductive agent hydrazine hydrate in the reduction pond, stir, and waste water recovery time in the reduction pond is sent into settling vessel after being 30min and carries out solid-liquid separation;
(4) the post precipitation clear liquid reaches integrated wastewater discharge standard (GB8978-1996), wherein 10% discharging, and 90% flows into middle wastewater disposal basin carries out subsequent disposal;
(5) the pH value with waste water in the middle wastewater disposal basin is adjusted to 6 ~ 6.5, NaHSO
3Dosage is 2mg/L, and the redox potential that makes waste water is about 400mV;
(6) utilize low-pressure pump that the waste water in the middle wastewater disposal basin is sent into more medium filter, more medium filter
Water outlet enters accurate filter, and the filter core aperture of accurate filter is 5 microns, removes suspended substance and colloid, makes pollution index SDI＜3;
(7) the accurate filter water outlet is sent into 1 section nanofiltration processing with high-pressure pump, and nanofiltration membrane can adopt the NF90 type nanofiltration membrane of DOW company, and the rate of recovery 60% of 1 section nanofiltration of control sees through liquid and is collected in the reuse water tank;
The dense water of (8) 1 sections nanofiltrations enters the reverse osmosis section by topping-up pump and handles, and reverse osmosis membrane can adopt the BW30-365FR pollution-resistant membrane, and the control reverse osmosis rate of recovery is 60%, and reverse osmosis sees through liquid and also is collected in the reuse water tank;
The dense water of (9) reverse osmosis section enters 2 sections nanofiltrations, and the nanofiltration membrane of 2 sections nanofiltrations can be selected the NF270 nanofiltration membrane of DOW company for use, and the rate of recovery control about 40% of 2 sections nanofiltrations sees through liquid and is back to middle wastewater disposal basin;
(10) 2 sections saturating dense water of nanofiltration (account for the former water yield about 10%) returns the wastewater disposal basin circular treatment.
Embodiment 2
A kind of cyanogen that contains contains chromium mixing electroplating wastewater, and the pH value is 8.8, and wherein total cyanide content is 31.5mg/L, and content of 6-valence Cr ions is 37.8mg/L, and total heavy metal ion content such as copper, zinc is 100 ~ 200mg/L.Because of the pH value of electroplating wastewater is 8.8, need not to regulate the pH value, concrete treatment step is as follows:
(1) starts O
3Producer is pressed O
3: CN
-(mass ratio) 5:1 feeds O
3, to stir, the controlled oxidation time is to enter the reduction pond behind the 60min;
(3) press hydrazine hydrate (N
2H
2H
2O) being 1:1 with chromic mass ratio adds the reductive agent hydrazine hydrate in the reduction pond, stir, and waste water recovery time in the reduction pond is sent into settling vessel after being 60min and carries out solid-liquid separation;
(4) the post precipitation clear liquid reaches integrated wastewater discharge standard (GB8978-1996), wherein 25% discharging, and 75% flows into middle wastewater disposal basin carries out subsequent disposal;
(5) the pH value with waste water in the middle wastewater disposal basin is adjusted to 6 ~ 6.5, NaHSO
3Dosage is 3mg/L, and the redox potential that makes waste water is about 350mV;
(6) utilize low-pressure pump that the waste water in the middle wastewater disposal basin is sent into fiber ball filter;
(7) water outlet of fiber ball filter enters accurate filter, and the filter core aperture of accurate filter is 5 microns,
Make pollution index SDI＜3;
(8) the accurate filter water outlet is sent into 1 section nanofiltration processing with high-pressure pump, and nanofiltration membrane can adopt the NF90 nanofiltration membrane of DOW company, and the rate of recovery 50% of 1 section nanofiltration of control sees through liquid and is collected in the reuse water tank;
The dense water of (9) 1 sections nanofiltrations enters the reverse osmosis section by topping-up pump and handles, and reverse osmosis membrane can adopt the BW30-400FR pollution-resistant membrane, and the control reverse osmosis rate of recovery is 50%, and reverse osmosis sees through liquid and also is collected in the reuse water tank;
The dense water of (10) reverse osmosis section enters 2 sections nanofiltrations, the nanofiltration membrane of 2 sections nanofiltrations can be selected the NF270 nanofiltration membrane of DOW company for use, the rate of recovery of 2 sections nanofiltrations control 30%, see through liquid be back in the middle of wastewater disposal basin, dense water (account for the former water yield about 18%) returns the wastewater disposal basin circular treatment.
Embodiment 3
A kind of cyanogen that contains contains chromium mixing electroplating wastewater, and the pH value is 9.2, and wherein total cyanide content is 51.3mg/L, and content of 6-valence Cr ions is 62.8mg/L, and total heavy metal ion contents such as total copper, total zinc, total chromium are greater than 200mg/L.Because of the pH value of electroplating wastewater is 9.2, need not to regulate the pH value, concrete treatment step is as follows:
(1) starts O
3Producer is pressed O
3: CN
-(mass ratio) 6:1 feeds O
3, to stir, the controlled oxidation time is to enter the reduction pond behind the 60min;
(3) press hydrazine hydrate (N
2H
2H
2O) being 1:1 with chromic mass ratio adds the reductive agent hydrazine hydrate in the reduction pond, stir, and waste water recovery time in the reduction pond is sent into settling vessel after being 60min and carries out solid-liquid separation;
(4) the post precipitation clear liquid reaches integrated wastewater discharge standard (GB8978-1996), wherein 35% discharging, and 65% flows into middle wastewater disposal basin carries out subsequent disposal;
(5) the pH value with waste water in the middle wastewater disposal basin is adjusted to 6 ~ 6.5, NaHSO
3Dosage is 4mg/L, and the redox potential that makes waste water is about 250mV;
(6) utilize low-pressure pump that the waste water in the middle wastewater disposal basin is sent into fabric filter;
(7) water outlet of fabric filter enters accurate filter, and the filter core aperture of accurate filter is 5 microns, makes
Pollution index SDI＜3;
(8) the accurate filter water outlet is sent into 1 section nanofiltration processing with high-pressure pump, and nanofiltration membrane can adopt the NF90 nanofiltration membrane of DOW company, and the rate of recovery 40% of 1 section nanofiltration of control sees through liquid and is collected in the reuse water tank;
The dense water of (9) 1 sections nanofiltrations enters the reverse osmosis section by topping-up pump and handles, and reverse osmosis membrane can adopt the BW30-4040FR pollution-resistant membrane, and the control reverse osmosis rate of recovery is 40%, and reverse osmosis sees through liquid and also is collected in the reuse water tank;
The dense water of (10) reverse osmosis section enters 2 sections nanofiltrations, the nanofiltration membrane of 2 sections nanofiltrations can be selected the NF270 nanofiltration membrane of DOW company for use, the rate of recovery of 2 sections nanofiltrations control 20%, see through liquid be back in the middle of wastewater disposal basin, dense water (account for the former water yield 29%) returns the wastewater disposal basin circular treatment.
Claims (5)
1. the treatment process of electroplating wastewater containing cyanogens and chrome is characterized in that comprising following processing step:
1) the pH value that cyanogen contains chromium mixing electroplating wastewater that contains in the broken cyanide pond is adjusted in 8.5 ~ 9.5;
2) start O
3Producer is pressed O
3: CN
-Mass ratio 4:1 ~ 6:1 feed O
3, to stir, the controlled oxidation time is to enter the reduction pond after 45 ~ 60 minutes;
3) press hydrazine hydrate (N
2H
2H
2O) being 0.75:1 ~ 1:1 with chromic mass ratio adds the reductive agent hydrazine hydrate in the reduction pond, stir, and waste water recovery time in the reduction pond is sent into settling vessel after being 30 ~ 60 minutes and carries out solid-liquid separation;
4) 10% ~ 30% qualified discharge of post precipitation clear liquid, 70% ~ 90% flows into middle wastewater disposal basin carries out subsequent disposal;
5) the pH value with waste water in the middle wastewater disposal basin is adjusted to 6 ~ 7, and adds NaHSO
3, controlled oxidation reduction potential 250 ~ 400mV;
6) utilize low-pressure pump that the waste water in the middle wastewater disposal basin is sent into medium filter and accurate filter, remove suspended substance and colloid, make pollution index SDI＜3;
7) water outlet of accurate filter is sent into 1 section nanofiltration processing with high-pressure pump, and the rate of recovery of 1 section nanofiltration is 40 ~ 60%, sees through liquid and is collected in the reuse water tank;
8) the dense water of 1 section nanofiltration enters the processing of reverse osmosis section by topping-up pump, and the rate of recovery is 40 ~ 60%, and reverse osmosis sees through liquid and is collected in the reuse water tank;
The dense water of 9) reverse osmosis section enters 2 sections nanofiltrations at last, and the liquid that sees through of 20 ~ 40%, 2 sections nanofiltrations of the rate of recovery of 2 sections nanofiltrations is back to the import of reverse osmosis section and carries out circular treatment;
10) with 2 sections saturating dense water of nanofiltration, account for 10% ~ 30% of the former water yield, return the raw water box circular treatment.
2. the treatment process of electroplating wastewater containing cyanogens and chrome according to claim 1 is characterized in that in the step 6), and described medium filter is a kind of in more medium filter, fiber ball filter, the fabric filter.
3. the treatment process of electroplating wastewater containing cyanogens and chrome according to claim 2, it is characterized in that in the step 7), the used nanofiltration membrane of described 1 section nanofiltration is the bear nanofiltration membrane, molecular weight cut-off is 100 ~ 150, the requirement of its separation performance is: in NaCl concentration is 2000mg/L, temperature is 25 ℃, and the operating pressure 0.48Mpa and the rate of recovery are under 15% the condition, the transmitance of NaCl＜5 ~ 15%.
4. the treatment process of electroplating wastewater containing cyanogens and chrome according to claim 2, it is characterized in that in the step 8), the used reverse osmosis membrane of described reverse osmosis is an anti-pollution reverse osmosis membrane, the requirement of its separation performance is: in NaCl concentration is 2000mg/L, temperature is 25 ℃, the operating pressure 1.0Mpa and the rate of recovery are under 15% the condition, the transmitance of NaCl＜1%.
5. according to the treatment process of the described electroplating wastewater containing cyanogens and chrome of one of claim 1 to 4, it is characterized in that in the step 9), the used nanofiltration membrane of described 2 sections nanofiltrations is the bear nanofiltration membrane, and molecular weight cut-off is 300 ~ 600, and the requirement of its separation performance is: at MgSO
4Concentration is 2000mg/L, and temperature is 25 ℃, and the operating pressure 0.48Mpa and the rate of recovery are under 15% the condition, MgSO
4Transmitance＜3%.
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| CN102101732A (en) * | 2011-01-14 | 2011-06-22 | 南京大学 | Method for recovering hydrazine sulfate and chromium hydroxide from chromium-containing waste acid |
| CN102320706A (en) * | 2011-07-08 | 2012-01-18 | 上海希沃环境科技有限公司 | System for deep recovery and treatment of coking wastewater biochemical effluent |
| CN102583831A (en) * | 2012-03-09 | 2012-07-18 | 广西宇达水处理设备工程有限公司 | Wastewater treatment and reusing membrane separation treatment technology |
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| CN102101732A (en) * | 2011-01-14 | 2011-06-22 | 南京大学 | Method for recovering hydrazine sulfate and chromium hydroxide from chromium-containing waste acid |
| CN102320706A (en) * | 2011-07-08 | 2012-01-18 | 上海希沃环境科技有限公司 | System for deep recovery and treatment of coking wastewater biochemical effluent |
| CN102775004A (en) * | 2011-10-31 | 2012-11-14 | 何学文 | Mixed electric plating wastewater treatment system and process method of mixed electric plating wastewater treatment system |
| CN102775004B (en) * | 2011-10-31 | 2014-03-12 | 何学文 | Mixed electric plating wastewater treatment system and process method of mixed electric plating wastewater treatment system |
| CN102583831A (en) * | 2012-03-09 | 2012-07-18 | 广西宇达水处理设备工程有限公司 | Wastewater treatment and reusing membrane separation treatment technology |
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| CN103395933A (en) * | 2013-08-02 | 2013-11-20 | 江苏和顺环保股份有限公司 | Processing technology for electroplating wastewater and heavy metal wastewater |
| CN103449571A (en) * | 2013-08-22 | 2013-12-18 | 煤炭科学研究总院杭州环保研究院 | Method and device for processing pit water |
| CN105152386A (en) * | 2015-05-18 | 2015-12-16 | 宣城得奇环保科技有限公司 | Mixed sewage treatment technology |
| CN106277420A (en) * | 2015-06-03 | 2017-01-04 | 中国科学院过程工程研究所 | A kind of dechromium method of organic reducing Cr VI alkaline waste liquor |
| CN106277420B (en) * | 2015-06-03 | 2019-07-23 | 中国科学院过程工程研究所 | A kind of dechromium method of organic reducing Cr VI alkaline waste liquor |
| CN107698108A (en) * | 2017-11-22 | 2018-02-16 | 天津海泽惠科技发展有限公司 | A kind of hydrazine hydrate utilization of wastewater resource device and its technique |
| CN109095564A (en) * | 2018-08-27 | 2018-12-28 | 浙江清华长三角研究院 | A kind of film advanced treatment process of drinking water |
| CN111762909A (en) * | 2020-07-17 | 2020-10-13 | 莱特莱德（北京）环境技术股份有限公司 | Device and method for treating and recycling gold-containing barren solution |
| CN113548757A (en) * | 2021-08-24 | 2021-10-26 | 山东建筑大学 | Zero-discharge treatment process for chromium-containing wastewater |
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| CN101875520B (en) | 2012-07-04 |
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