CN102120668A - Printed circuit board integrated wastewater resource utilization method - Google Patents
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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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- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010802 sludge Substances 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 14
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- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000004062 sedimentation Methods 0.000 claims abstract description 10
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000005189 flocculation Methods 0.000 claims abstract description 4
- 230000016615 flocculation Effects 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 3
- 239000004576 sand Substances 0.000 claims abstract 2
- 238000005345 coagulation Methods 0.000 claims description 10
- 230000015271 coagulation Effects 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 9
- 239000000701 coagulant Substances 0.000 claims description 8
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
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- 235000010755 mineral Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 238000010979 pH adjustment Methods 0.000 abstract 1
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- 239000005446 dissolved organic matter Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
印刷线路板综合废水资源化利用方法是应用于印刷线路板(PCB)企业产生的线路板综合废水处理与资源回收的一套完整的工艺体系。PCB综合废水经pH调节池、絮凝池、沉淀池、生物活性滤池、超滤和反渗透工艺的预处理和深度处理后，出水水质可回用于生产线用水，生物活性滤池采用多层介质，取代常规的砂滤池和活性炭池串联工艺，既可保证对于悬浮物的物理过滤效果，又具有生物降解有机物的功能。沉淀池分离出的泥进入污泥浓缩池进行浓缩，浓缩后的泥经气隔离泵进入贮泥罐、厢式压滤机，压滤后的污泥体积降低，经过焙烧纯化、粉碎、酸浸过程后，污泥中的金属铜离子完全转移到酸溶液中。含铜酸液经过电解可以回收品质较好的金属铜和硫酸溶液。
The resource utilization method of printed circuit board comprehensive wastewater is a complete process system applied to the treatment and resource recovery of circuit board comprehensive wastewater generated by printed circuit board (PCB) enterprises. After pretreatment and advanced treatment of PCB comprehensive wastewater by pH adjustment tank, flocculation tank, sedimentation tank, biological active filter, ultrafiltration and reverse osmosis process, the effluent quality can be reused for production line water, and the biological active filter adopts multi-layer media , instead of the conventional sand filter and activated carbon pool series process, it can not only ensure the physical filtration effect on suspended solids, but also have the function of biodegrading organic matter. The sludge separated from the sedimentation tank enters the sludge concentration tank for concentration, and the concentrated sludge enters the sludge storage tank and chamber filter press through the air isolation pump. After the process, the metal copper ions in the sludge are completely transferred to the acid solution. The copper-containing acid solution can be electrolyzed to recover metal copper and sulfuric acid solution with better quality.
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 |
| 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 |
| CN106242118A (en) * | 2016-08-30 | 2016-12-21 | 上海交通大学 | Boracic treatment of Phosphorus Containing Waste Water system |
| 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 |
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| 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 |