CN102120668A - Printed circuit board integrated wastewater resource utilization method - Google Patents
Printed circuit board integrated wastewater resource utilization method Download PDFInfo
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- CN102120668A CN102120668A CN2010102917801A CN201010291780A CN102120668A CN 102120668 A CN102120668 A CN 102120668A CN 2010102917801 A CN2010102917801 A CN 2010102917801A CN 201010291780 A CN201010291780 A CN 201010291780A CN 102120668 A CN102120668 A CN 102120668A
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Abstract
A printed circuit board (PCB) integrated wastewater resource utilization method is used in a complete process system of PCB integrated wastewater treatment and resource utilization used in the PCB enterprise. The method is as follows: the PCB integrated wastewater performs the pretreatment and advanced treatment adopting a pH adjusting tank, a flocculating tank, a setting tank, a biological activated filter and an ultrafiltration and reverse osmosis process, and the effluent can be reused as the production line water; and the biological activated filter uses multiple layers of medium to replace the conventional combined process of the sand filter and the activated carbon tank, thus the physical filtering effect of the suspended matter can be ensured and the organic matter can be degraded through biological method. The mud separated by the setting tank enters a sludge concentration tank to concentrate, the concentrated mud enters a mud storage tank and a box-type filter press through an air isolation pump, the volume of the pressed sludge is reduced, after the obtained mud is roasted, purified, crushed and soaked in acid, the copper ions in the sludge are completely transferred to the acidic solution. The acidic solution containing copper is electrolyzed to recycle copper and sulfuric acid which have better qualities.
Description
Technical field
The present invention is a field of environment engineering Industrial Wastewater Treatment engineering, especially is applied to the printed-wiring board (PWB) comprehensive wastewater and handles the advanced technologies that reclaims with resource, belongs to technical field of environment protection.
Technical background
In recent years, along with the fast development of electronic industry, the demand of printed-wiring board (PWB) (printed circuit board abbreviates PCB as) is increased greatly, the production of PCB has become the important foundation industry of electron trade.China's electronic industry develop rapidly, the PCB industry output value increases with about 20% every year, by 2006 just with the nearly 13,000,000,000 dollars output value using names whole world first big producing country.The PCB industry is the water rich and influential family, also is simultaneously to produce the waste water rich and influential family, and environmental pollution is serious.At present, printed-wiring board (PWB) factory comprehensive wastewater mainly is to handle directly discharging of back through simple coagulating sedimentation and bio-contact oxidation, and this process combination floor space in actual applications is big, and sludge output is big, and waste water can not recycle.
Therefore, carrying out PCB comprehensive wastewater resource technology research and development, realize the water resources recycle and reclaim cupric ion in the waste water, is to realize the Sustainable development important channel, can save a large amount of water sources, solves the difficult problem of enterprise water use; And the recovery of valuable copper resource, can save enterprise cost, alleviate environmental pollution, be the basic outlet that guarantees the PCB industrial sustainable development.Utilization PCB comprehensive wastewater resource technology can be realized the zero release of PCB comprehensive wastewater, reaches the purpose that social benefit, environmental benefit, economic benefit develop simultaneously.
Summary of the invention
Technical problem: the purpose of this invention is to provide the method for utilizing that a cover satisfies maximum resourceization that the water resources reuse of printed-wiring board (PWB) comprehensive wastewater and cupric ion reclaim.
Technical scheme: the present invention is the conventional pretreated technology of in-depth printed-wiring board (PWB) comprehensive wastewater, and uses two groups of technologies on this basis and realize that respectively water resources reuse and copper reclaim.Can realize the recycling of water resources after the operations such as printed-wiring board (PWB) comprehensive wastewater process pH regulator pond, coagulating sedimentation, bioactivity filter, ultrafiltration, reverse osmosis, reach the resource utilization of waste water.PH regulator and coagulation stage add an amount of alkali or acid and an amount of coagulating agent and coagulant aids respectively because of the water quality different needs in waste water.The coagulating sedimentation unit mainly is to remove suspended substance and separating copper ion from water.The settling tank water outlet enters bioactivity filter (being made up of the multilayered medium that comprises quartz sand and gac), and suspended particulate is tackled in sand filtration effectively, and gac is brought into play the effect of absorption and degraded simultaneously, reduces organic concentration.Content of copper ion height in the PCB comprehensive wastewater, the settling tank sludge yield is big, and the mud that precipitation produces enters sludge thickener, handles through operations such as press filtration, roasting purifying, pulverizing, acidleach pond, electrolyzers to storage mud jar through pneumatic diaphragm pump again.The acidleach process need add finite concentration sulfuric acid, guarantees that the cupric ion in the mud dissolves fully.Electrolyzer is realized the recovery of acid and cupric ion, restored acid can recycle in the acidleach pond, effectively reduced consumption sour in a whole set of technology; The copper purity height that reclaims, quality better can apply in the production technique of wiring board again.The treatment process of above-mentioned PCB comprehensive wastewater has demonstrated fully the theory of recycling and recycling economy, can be used as China and solves the useful of shortage of resources problem and replenish.
This technological invention is reclaimed (circuit 1) and metallic copper by water resources and is reclaimed (circuit 2) and totally two overlap parallel connection technologies and form.Wherein the water resources recovery train is: pH regulator pond-coagulating sedimentation-bioactivity filter-ultrafiltration-reverse osmosis process combination is specially:
1) pH regulator pond: the printed-wiring board (PWB) comprehensive wastewater mainly is strongly-acid, contains a large amount of cupric ions in the water, can realize the precipitation of maximum for guaranteeing cupric ion under best pH condition, need add liquid caustic soda in the water of source, is adjusted to about pH=8;
2) coagulating sedimentation: the water outlet in pH regulator pond enters coagulation basin, determine the best dosage of coagulating agent and coagulant aids according to the content of cupric ion in the test waste water, utilization automatic chemical dosing device adds, also need to control the mechanical stirring speed difference 30.0r/min of flocculation basin three lattice simultaneously, 22.0r/min, 13.0r/min, settling tank carries out mud-water separation, water outlet enters bioactivity filter, and mud enters sludge thickener;
3) bioactivity filter filters: bioactivity filter is by the bottom filling supporting layer, and homogeneous quartz filler and active carbon filler are formed, and the height of supporting layer, quartz sand and gac is respectively 300mm, 350mm and 650mm; From the water outlet of coagulating sedimentation, after bioactivity filter filtered, water outlet entered ultrafiltration;
4) ultrafiltration: water outlet is handled to bioactivity filter, and colloid, particle and larger molecular organics in the trap water guarantee feed water by reverse osmosis water quality;
5) reverse osmosis: the various mineral ions in the trap water, colloidalmaterial and macromole solute, reduce electrical conductivity of water, guarantee that effluent quality satisfies the reuse water requirement;
The metallic copper recovery train is: sludge thickener bed mud-press filtration-roasting purifying-pulverizing-acidleach-electrolysis process combination is specially:
1) sludge thickener: settling tank bed mud water ratio is very high, mud need be concentrated for reducing sludge volume, and the concentration basin supernatant liquor is gone into bioactivity filter, the treatment system of entry-line 1;
2) press filtration: spissated mud enters storage mud jar by pneumatic separate pump and carries out press filtration again, reduces the water ratio of mud, dwindles and deposits volume;
3) roasting purifying: the control maturing temperature is 600 ℃, by moisture and the organism in the roasting removal mud;
4) acidleach: be dissolved in the sulfuric acid after the pulverizing with mud after the roasting, the copper sludge of every 500g needs the sulfuric acid dissolution of 10L 6mol/L, and this moment, cupric ion was transferred to from mud in the acid solution fully, for increasing dissolution rate, was heated to 90 ℃;
5) electrolysis: filtering the laggard capable electrolysis of acid solution is recyclable metallic copper and sulfuric acid, and the sulfuric acid of recovery is used for acidleach once more.
Beneficial effect: the resource utilization method system of PCB comprehensive wastewater involved in the present invention is complete, make PCB waste water reclaiming, innoxious, realized the recycling of resource, the zero release of pollutent, non-secondary pollution in its treating processes has embodied the unification of social benefit, environmental benefit, economic benefit.
Description of drawings
Fig. 1 is printed-wiring board (PWB) comprehensive wastewater resource utilization process flow figure.
Embodiment
1) pH regulator: generally between 2～3, equalizing tank is provided with automatic on-line control pH device and stirrer to the pH of PCB comprehensive wastewater, raises about pH to 8, guarantees the optimal coagulation deposition condition of cupric ion.
2) coagulating sedimentation: the water outlet of pH regulator pond is squeezed into elevated tank by pump, flow into coagulation basin through elevated tank, before water entered coagulation basin, coagulating agent PAC and coagulant aids PAM added in the pipeline of coagulation basin front end by volume pump, and the concentration of PAC and PAM is respectively 5% and 0.1%.The machinery coagulation basin is divided into three lattice, and the revolution of impeller can be regulated according to the water yield and water quality, and the revolution of paddle wheel single-frame reduces, and is beneficial to the formation of flocs unit.With the vertical partition wall water conservancy diversion that is provided with water hole, interlace mode arrangement is up and down taked in the position, aperture, and current are evenly distributed between each lattice of coagulation basin.The coagulation basin water outlet directly enters inclined-plate clarifying basin, and mud enters sludge thickener.
3) bioactivity filter: the settling tank water outlet enters bioactivity filter, and bioactivity filter is by the bottom filling supporting layer, and quartz sand filler and active carbon filler are formed.Bioactivity filter utilization natural membrane, the empty bed residence time is about 15min.According to the effluent quality situation mode of filter tank utilization combined water and air backwash is carried out back flushing.
(4) ultrafiltration: the bioactivity filter water outlet enters ultra filtration unit.Ultrafiltration fenestra aperture 0.005-0.1 can remove particulate in the water, colloidalmaterial and bacterium, and clearance can reach 99.9%; Saturating film pressure is less than 0.1MPa, delivery turbidity＜0.2NTU, SDI＜3.As the reverse osmosis pre-treatment time, operating pressure is 0.1-0.2MPa.
5) reverse osmosis: the ultrafiltration water outlet enters reverse osmosis units, and the reverse osmosis membrane aperture is on the 10 Izod right sides, and working pressure is 1-10MPa, and it can remove the most materials in the water, as suspended substance, dissolved organic matter, inorganic salt, bacterium, colloid, microorganism etc.Reverse osmosis goes out water conductivity less than 100 μ S/cm, can satisfy production line water water quality requirement.
6) mud concentrates press filtration: the settling tank bed mud enters sludge thickener, lowers water ratio, squeezes into the filter of storage mud tank pressure by pneumatic separate pump, and mud is block after the press filtration, and water ratio is about 65%.Concentrating the supernatant liquor that produces with compression process returns flocculation basin or directly enters the bioactivity filter processing.
7) roasting purifying: the mud after the press filtration is in the stoving oven roasting, and the control maturing temperature is 600 ℃, and moisture and organism can burn mistake after the roasting, and this process energy consumption is low.
8) acidleach: the mud after the roasting is ground into Powdered being dissolved into again in the 6mol/L sulfuric acid through pulverizer, and this process can be heated to 90 ℃, and the accelerate dissolution process is transferred in the acid solution cupric ion fully.
9) electrolysis: filter acid solution, remove a small amount of residue.Electrolytic cell anode is a graphite electrode plate, and negative electrode is a stainless steel plate, and electrolyzer is furnished with agitator, and metallic copper is directly separated out at negative electrode, and the debris main component is that sulfuric acid can be back to use step 9).
Claims (3)
1. printed-wiring board (PWB) comprehensive wastewater resource utilization method, it is characterized in that this method comprises water resources recovery train and metallic copper recovery train, wherein the water resources recovery train is: pH regulator pond-coagulating sedimentation-bioactivity filter-ultrafiltration-reverse osmosis process combination is specially:
1) pH regulator pond: the printed-wiring board (PWB) comprehensive wastewater mainly is strongly-acid, contains a large amount of cupric ions in the water, can realize the precipitation of maximum for guaranteeing cupric ion under best pH condition, need add liquid caustic soda in the water of source, is adjusted to about pH=8;
2) coagulating sedimentation: the water outlet in pH regulator pond enters coagulation basin, determine the best dosage of coagulating agent and coagulant aids according to the content of cupric ion in the test waste water, utilization automatic chemical dosing device adds, also need to control the mechanical stirring speed difference 30.0r/min of flocculation basin three lattice simultaneously, 22.0r/min, 13.0r/min, settling tank carries out mud-water separation, water outlet enters bioactivity filter, and mud enters sludge thickener;
3) bioactivity filter filters: bioactivity filter is by the bottom filling supporting layer, and homogeneous quartz filler and active carbon filler are formed, and the height of supporting layer, quartz sand and gac is respectively 300mm, 350mm and 650mm; From the water outlet of coagulating sedimentation, after bioactivity filter filtered, water outlet entered ultrafiltration;
4) ultrafiltration: water outlet is handled to bioactivity filter, and colloid, particle and larger molecular organics in the trap water guarantee feed water by reverse osmosis water quality;
5) reverse osmosis: the various mineral ions in the trap water, colloidalmaterial and macromole solute, reduce electrical conductivity of water, guarantee that effluent quality satisfies the reuse water requirement;
The metallic copper recovery train is: sludge thickener bed mud-press filtration-roasting purifying-pulverizing-acidleach-electrolysis process combination is specially:
1) sludge thickener: settling tank bed mud water ratio is very high, mud need be concentrated for reducing sludge volume, and the concentration basin supernatant liquor is gone into bioactivity filter, the treatment system of entry-line 1;
2) press filtration: spissated mud enters storage mud jar by pneumatic separate pump and carries out press filtration again, reduces the water ratio of mud, dwindles and deposits volume;
3) roasting purifying: the control maturing temperature is 600 ℃, by moisture and the organism in the roasting removal mud;
4) acidleach: be dissolved in the sulfuric acid after the pulverizing with mud after the roasting, the copper sludge of every 500g needs 10L
The sulfuric acid dissolution of 6mol/L, this moment, cupric ion was transferred to from mud in the acid solution fully, for increasing dissolution rate, was heated to 90 ℃;
5) electrolysis: filtering the laggard capable electrolysis of acid solution is recyclable metallic copper and sulfuric acid, and the sulfuric acid of recovery is used for acidleach once more.
2. printed-wiring board (PWB) comprehensive wastewater resource utilization method according to claim 1, it is characterized in that: set up bioactivity filter to replace conventional sand filter+biological activated carbon filter in the water resources recovery train, bioactivity filter is made up of supporting layer, homogeneous quartz sand and gac, the assurance bioactivity filter is realized filtering simultaneously, absorption and degradation function.
3. printed-wiring board (PWB) comprehensive wastewater resource utilization method according to claim 1 is characterized in that: utilization roasting purifying process in the metal recovery circuit, and the control maturing temperature is 600 ℃, saves energy consumption; Electrolysis cells realizes that simultaneously metallic copper and sulphuric acid soln reclaim, and the metallic copper of recovery is used for wiring board production, and restored acid liquid is back to the acidleach pond.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358644A (en) * | 2011-06-28 | 2012-02-22 | 中南大学 | Membrane treatment process for heavy metal waste water generated during PCB production process |
| CN102583619A (en) * | 2012-01-19 | 2012-07-18 | 靖德兵 | Method for removing heavy metal in water by utilizing plant-biomass composite adsorbent |
| CN104176854A (en) * | 2014-08-21 | 2014-12-03 | 营口东吉科技（集团）有限公司 | Method for utilizing mineral separation backwater in magnesite reverse flotation desilicification |
| CN104556469A (en) * | 2013-10-25 | 2015-04-29 | 北大方正集团有限公司 | Organic waste liquid treatment method |
| CN104829003A (en) * | 2015-04-24 | 2015-08-12 | 刘宝成 | Copper-containing industrial waste liquid recycling method |
| CN105060581A (en) * | 2015-08-28 | 2015-11-18 | 上海八菱环保科技有限公司 | Treatment system and method for dark brown wastewater |
| CN105523668A (en) * | 2015-12-04 | 2016-04-27 | 陈丽珊 | PCB ammonia-nitrogen wastewater zero discharge treatment method and device thereof |
| CN106222422A (en) * | 2016-08-22 | 2016-12-14 | 南昌航空大学 | A kind of rich in heavy metal biological precipitation slag short route metal smelt recovery new method |
| CN106242118A (en) * | 2016-08-30 | 2016-12-21 | 上海交通大学 | Boracic treatment of Phosphorus Containing Waste Water system |
| CN106242187A (en) * | 2016-08-31 | 2016-12-21 | 南京河海环境研究院有限公司 | Sewage purification circulation utilizes device |
| CN108002595A (en) * | 2017-12-22 | 2018-05-08 | 星华科技（惠州）有限公司 | A kind of wiring board comprehensive effluent disposal technology |
| CN108249670A (en) * | 2018-01-16 | 2018-07-06 | 张家港市佰坤物资有限公司 | A kind of acid etching liquid treatment acid solution and the technique for recycling copper |
| CN109467241A (en) * | 2018-10-29 | 2019-03-15 | 深圳骏泽环保有限公司 | The board wastewater treatment process of copper ion zero-emission |
| CN111559808A (en) * | 2020-05-12 | 2020-08-21 | 广德华东电子电路发展有限公司 | Treatment process for recovering copper from wastewater of PCB production line |
| CN113443784A (en) * | 2021-06-25 | 2021-09-28 | 铜陵有色金属集团股份有限公司 | Method for recovering copper ions in copper ore wastewater by using coagulation method |
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2010
- 2010-09-26 CN CN2010102917801A patent/CN102120668A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358644A (en) * | 2011-06-28 | 2012-02-22 | 中南大学 | Membrane treatment process for heavy metal waste water generated during PCB production process |
| CN102583619A (en) * | 2012-01-19 | 2012-07-18 | 靖德兵 | Method for removing heavy metal in water by utilizing plant-biomass composite adsorbent |
| CN104556469A (en) * | 2013-10-25 | 2015-04-29 | 北大方正集团有限公司 | Organic waste liquid treatment method |
| CN104176854A (en) * | 2014-08-21 | 2014-12-03 | 营口东吉科技（集团）有限公司 | Method for utilizing mineral separation backwater in magnesite reverse flotation desilicification |
| CN104829003A (en) * | 2015-04-24 | 2015-08-12 | 刘宝成 | Copper-containing industrial waste liquid recycling method |
| CN104829003B (en) * | 2015-04-24 | 2016-12-07 | 温州金源化工有限公司 | A kind of recoverying and utilizing method of cupric industrial wastes |
| CN105060581A (en) * | 2015-08-28 | 2015-11-18 | 上海八菱环保科技有限公司 | Treatment system and method for dark brown wastewater |
| CN105523668A (en) * | 2015-12-04 | 2016-04-27 | 陈丽珊 | PCB ammonia-nitrogen wastewater zero discharge treatment method and device thereof |
| CN106222422A (en) * | 2016-08-22 | 2016-12-14 | 南昌航空大学 | A kind of rich in heavy metal biological precipitation slag short route metal smelt recovery new method |
| CN106242118A (en) * | 2016-08-30 | 2016-12-21 | 上海交通大学 | Boracic treatment of Phosphorus Containing Waste Water system |
| CN106242187A (en) * | 2016-08-31 | 2016-12-21 | 南京河海环境研究院有限公司 | Sewage purification circulation utilizes device |
| CN108002595A (en) * | 2017-12-22 | 2018-05-08 | 星华科技（惠州）有限公司 | A kind of wiring board comprehensive effluent disposal technology |
| CN108249670A (en) * | 2018-01-16 | 2018-07-06 | 张家港市佰坤物资有限公司 | A kind of acid etching liquid treatment acid solution and the technique for recycling copper |
| CN109467241A (en) * | 2018-10-29 | 2019-03-15 | 深圳骏泽环保有限公司 | The board wastewater treatment process of copper ion zero-emission |
| CN111559808A (en) * | 2020-05-12 | 2020-08-21 | 广德华东电子电路发展有限公司 | Treatment process for recovering copper from wastewater of PCB production line |
| CN113443784A (en) * | 2021-06-25 | 2021-09-28 | 铜陵有色金属集团股份有限公司 | Method for recovering copper ions in copper ore wastewater by using coagulation method |
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Application publication date: 20110713 |