CN101875520B - 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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- CN101875520B CN101875520B CN2010102490276A CN201010249027A CN101875520B CN 101875520 B CN101875520 B CN 101875520B CN 2010102490276 A CN2010102490276 A CN 2010102490276A CN 201010249027 A CN201010249027 A CN 201010249027A CN 101875520 B CN101875520 B CN 101875520B
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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 article 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 type 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 to the rinse water of single plating kind, are inappropriate 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 the single collection 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 greatlyyer, energy consumption is high, does not announce the treatment process of dense water.
Summary of the invention
To the shortcoming of prior art, the technical problem that the present invention will solve 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 process 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 get into the reduction pond after 45 ~ 60 minutes;
3) press Hydrazine Hydrate 80 (N
2H
2H
2O) being 0.75:1 ~ 1:1 with chromic mass ratio adds the reductive agent Hydrazine Hydrate 80 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 HPP, and the 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 gets into the processing of r-o-section through topping-up pump, and the recovery is 40 ~ 60%, and r-o-sees through liquid and is collected in the reuse water tank;
The dense water of 9) r-o-section is last to get into 2 sections nanofiltrations, and the liquid that sees through of 20 ~ 40%, 2 sections nanofiltrations of the recovery of 2 sections nanofiltrations is back to the import of r-o-section and carries out circular treatment;
10) dense water is passed through in 2 sections nanofiltrations, 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 silica sand), fiber ball filter (filtration medium is a fibrous nodules), the fabric filter (filtration medium is a fiber).
1 section used nf 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 recovery are under 15% the condition, the transmitance < 5 ~ 15% of NaCl.
The used reverse osmosis membrane of r-o-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 recovery are under 15% the condition, the transmitance < 1% of NaCl.
2 sections used nf 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 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 r-o-operation, also reduced processing cost; (3) appropriate design through nanofiltration and r-o-; Make 1 section nanofiltration see through liquid and r-o-see through all ability direct reuses of liquid; The required working pressure of r-o-has made full use of the overbottom pressure of 1 section dense water of nanofiltration, makes 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 accompanying drawing and specific embodiment, the present invention is explained 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 that 45 minutes (min) back gets into the reduction pond;
(3) press Hydrazine Hydrate 80 (N
2H
2H
2O) being 0.75:1 with chromic mass ratio adds the reductive agent Hydrazine Hydrate 80 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 gets into 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 HPP, and nf membrane can adopt the NF90 type nf membrane of DOW company, and the 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 gets into the r-o-section through topping-up pump and handles, and reverse osmosis membrane can adopt the BW30-365FR pollution-resistant membrane, and the control r-o-recovery is 60%, and r-o-sees through liquid and also is collected in the reuse water tank;
The dense water of (9) r-o-section gets into 2 sections nanofiltrations, and the nf membrane of 2 sections nanofiltrations can be selected the NF270 nf membrane of DOW company for use, and the recovery control about 40% of 2 sections nanofiltrations sees through liquid and is back to middle wastewater disposal basin;
(10) 2 sections nanofiltrations are passed through dense water (account for the former water yield about 10%) and are returned 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 37.8 mg/L, and total heavy metal ion content such as copper, zinc is 100 ~ 200 mg/L.Because of the pH value of electroplating wastewater is 8.8, need not to regulate the pH value, concrete treatment step is following:
(1) starts O
3Producer is pressed O
3: CN
-(mass ratio) 5:1 feeds O
3, to stir, the controlled oxidation time is to get into the reduction pond behind the 60min;
(3) press Hydrazine Hydrate 80 (N
2H
2H
2O) being 1:1 with chromic mass ratio adds the reductive agent Hydrazine Hydrate 80 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 gets into 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 HPP, and nf membrane can adopt the NF90 nf membrane of DOW company, and the 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 gets into the r-o-section through topping-up pump and handles, and reverse osmosis membrane can adopt the BW30-400FR pollution-resistant membrane, and the control r-o-recovery is 50%, and r-o-sees through liquid and also is collected in the reuse water tank;
The dense water of (10) r-o-section gets into 2 sections nanofiltrations; The nf membrane of 2 sections nanofiltrations can be selected the NF270 nf membrane of DOW company for use; The 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 62.8 mg/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 following:
(1) starts O
3Producer is pressed O
3: CN
-(mass ratio) 6:1 feeds O
3, to stir, the controlled oxidation time is to get into the reduction pond behind the 60min;
(3) press Hydrazine Hydrate 80 (N
2H
2H
2O) being 1:1 with chromic mass ratio adds the reductive agent Hydrazine Hydrate 80 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 gets into 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 HPP, and nf membrane can adopt the NF90 nf membrane of DOW company, and the 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 gets into the r-o-section through topping-up pump and handles, and reverse osmosis membrane can adopt the BW30-4040FR pollution-resistant membrane, and the control r-o-recovery is 40%, and r-o-sees through liquid and also is collected in the reuse water tank;
The dense water of (10) r-o-section gets into 2 sections nanofiltrations; The nf membrane of 2 sections nanofiltrations can be selected the NF270 nf membrane of DOW company for use; The 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 process step:
1) the pH value with the electroplating wastewater containing cyanogens and chrome 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 get into the reduction pond after 45 ~ 60 minutes;
3) press Hydrazine Hydrate 80 (N
2H
2H
2O) being 0.75:1 ~ 1:1 with chromic mass ratio adds the reductive agent Hydrazine Hydrate 80 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 HPP, and the 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 gets into the processing of r-o-section through topping-up pump, and the recovery is 40 ~ 60%, and r-o-sees through liquid and is collected in the reuse water tank;
The dense water of 9) r-o-section is last to get into 2 sections nanofiltrations, and the liquid that sees through of 20 ~ 40%, 2 sections nanofiltrations of the recovery of 2 sections nanofiltrations is back to the import of r-o-section and carries out circular treatment;
10) dense water is passed through in 2 sections nanofiltrations, 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) that the used nf 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 recovery are under 15% the condition, the transmitance < 5 ~ 15% of NaCl.
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 r-o-is an anti-pollution reverse osmosis membrane, and the requirement of its separation performance is: in NaCl concentration is 2000mg/L, and temperature is 25 ℃; The operating pressure 1.0Mpa and the recovery are under 15% the condition, the transmitance < 1% of NaCl.
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 nf 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 recovery are under 15% the condition, MgSO
4Transmitance<3%.
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|---|---|---|---|
| CN2010102490276A CN101875520B (en) | 2010-08-10 | 2010-08-10 | Processing method of electroplating wastewater containing cyanogens and chrome |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102490276A CN101875520B (en) | 2010-08-10 | 2010-08-10 | Processing method of electroplating wastewater containing cyanogens and chrome |
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| Publication Number | Publication Date |
|---|---|
| CN101875520A CN101875520A (en) | 2010-11-03 |
| CN101875520B true CN101875520B (en) | 2012-07-04 |
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Cited By (1)
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|---|---|---|---|---|
| WO2014194664A1 (en) * | 2013-06-04 | 2014-12-11 | 长春黄金研究院 | Method for treating wastewater containing cyanides, thiocyanides and heavy metals |
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| 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 |
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| 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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| JP4373700B2 (en) * | 2002-06-05 | 2009-11-25 | 三菱電機株式会社 | Organic waste liquid processing method and processing apparatus |
| MXPA06007148A (en) * | 2006-06-21 | 2007-04-23 | Alcocer Juan Jorge Diaz Gonzal | Integral method and system useful for treating cooling tower water and processes for removing silica from water. |
| CN101239769B (en) * | 2008-02-01 | 2011-05-25 | 浙江大学 | Leather-making waste water reusing treatment method |
| CN101774725A (en) * | 2009-01-13 | 2010-07-14 | 厦门市威士邦膜科技有限公司 | Electroplating wastewater treatment process and equipment |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014194664A1 (en) * | 2013-06-04 | 2014-12-11 | 长春黄金研究院 | Method for treating wastewater containing cyanides, thiocyanides and heavy metals |
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