CN102503009A - Recycling method of chemical copper plating waste liquid - Google Patents

Recycling method of chemical copper plating waste liquid Download PDF

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Publication number
CN102503009A
CN102503009A CN2011103011199A CN201110301119A CN102503009A CN 102503009 A CN102503009 A CN 102503009A CN 2011103011199 A CN2011103011199 A CN 2011103011199A CN 201110301119 A CN201110301119 A CN 201110301119A CN 102503009 A CN102503009 A CN 102503009A
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China
Prior art keywords
waste liquid
groove
copper
copper sulfate
tank
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Pending
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CN2011103011199A
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Chinese (zh)
Inventor
万孝树
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CHENGDU DAZHONGHUA WELDING MATERIAL Co Ltd
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CHENGDU DAZHONGHUA WELDING MATERIAL Co Ltd
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Priority to CN2011103011199A priority Critical patent/CN102503009A/en
Publication of CN102503009A publication Critical patent/CN102503009A/en
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Abstract

The invention discloses a recycling method of a chemical copper plating waste liquid. The method is characterized by comprising the following steps of: (1) collecting the copper sulfate waste liquid discharged from a production system, in a waste liquid storage tank for later use; (2) pumping the copper sulfate waste liquid of the waste liquid storage tank in an Fe<2+> removing tank; (3) heating the waste liquid in the Fe<2+> removing tank at 60-70 DEG C, adding CaCO3 to ensure that the pH value of the solution is adjusted to 2-3, then adding hydrogen peroxide in the Fe<2+> removing tank to ensure that Fe<2+> is converted into Fe<3+>, adding Na2SO4, performing mechanical agitation for 1-2 hours to fully react and generate ferrovanadium; (4) filtering and removing ferrovanadium obtained in the step (3), introducing the filtered copper sulfate solution in a liquid tank, wherein each index of the copper sulfate solution is to be tested; and (5) testing each index of copper sulfate in the liquid tank. By adopting the treatment in the steps, the copper sulfate solution for the production of the gas shielded welding wire can completely realize self-circulation recycling, the production cost can be reduced and the pollution of the copper ions (heavy metal) to the environment can be eliminated; and the method is beneficial to both the nation and people.

Description

A kind of recoverying and utilizing method of Chemical Copper Plating Effluent
Technical field
The present invention relates to the recycling field of Chemical Copper Plating Effluent, specifically the recoverying and utilizing method of copper facing waste liquid.
Background technology
Continuous development along with China's industry; Especially the development of China's welding technique and welding material; The production of China's solid wire accounts for global over half; Because solid wire must carry out copper plating treatment on its surface in process of production, have satisfactory electrical conductivity and anti-atmospheric oxidation in use.The production process of real core gas protecting welding wire the technology of its surface by utilizing electroless copper be copper and iron directly change reaction, in the copper facing process, Cu ++Ion reduces, Fe ++Ionic concn raises, and works as Cu ++Ionic concn is lower than when a certain amount of, and the copper facing process can not normally be carried out, and therefore must add Cu SO 4Solution.And Fe ++Ionic concn when a certain amount of, can not make the copper facing process normally carry out greater than certain.Therefore must be with Fe ++Ion surpasses certain density liquid and discharges production line, replenishes new plating bath.Generally be after waste collection is carried out harmless treatment to it in the blowdown pond, discharging.Operation can make the Cu in the waste liquid waste with the discharging of the form of slag like this, not only diminishes environment but also waste resource.
The patent No. is 88106916 Chinese invention patent; The method of iron removal by oxidation reclaim(ed) sulfuric acid copper waste liquid in a kind of chemical dumpling process for copper is disclosed; Specifically be characterised in that, with pressurized air with in the vaporific people of the blowing bluestone waste to be recycled. simultaneously this waste liquid is heated to>90 ℃.And adding Na 2CO 3(or NaOH) transfers to 1.2～1.5 with the pH value solution, adds Na again 2SO 3, its consumption is can guarantee to generate ihleite NaFe 3(SO 4) 2(OH) 6Precipitating required Na ion is as the criterion.Fully stirred then 4 hours, and after the deposition sedimentation to be generated, isolated supernatant liquid, with it as the copper-bath that recycles.Foregoing invention adopts air as oxygenant, and said waste liquid need be heated to>90 ℃, yet in operating process since the air blowing meeting a large amount of take away heat, keep temperature＞90 ℃ of reaction, need a large amount of additional heat, so energy consumption is high.
Summary of the invention
The object of the present invention is to provide a kind of recoverying and utilizing method of Chemical Copper Plating Effluent, mainly solve FeSO 4During concentration>=60g/L, the deironing problem of the useless copper plating bath of discharge, and make the recycling that reaches Chemical Copper Plating Effluent, chemical-copper-plating process waste liquid do not discharge, free from environmental pollution.
The present invention is achieved in that the recoverying and utilizing method of a kind of Chemical Copper Plating Effluent of structure, it is characterized in that:
(1): collect in the waste liquid deposit groove bluestone waste that discharges in the production system subsequent use;
(2): the bluestone waste suction that waste liquid is laid in the groove removes Fe ++In the groove;
(3): will be except that Fe ++Waste liquid heats in the groove, and Heating temperature is 60～70 ℃, and next adds CaCO 3Make the solution pH value transfer to 2～3, removing Fe then ++Add ydrogen peroxide 50 in the groove, through ydrogen peroxide 50 with Fe ++Be converted into Fe +++, add Na 2SO 4, carry out mechanical stirring and it was fully reacted in 1～2 hour, make it generate yellow ferrovanadium;
(4): yellow ferrovanadium in the step 3 is filtered removing, and copper-bath after filtering enters into each item index that liquid storage groove waits to chemically examine copper-bath;
(5): copper sulfate each item index of inspection chemical examination liquid storage groove, like Fe ++Below standard must returning to removed Fe ++Carry out secondary treatment in the groove, like Fe +++Ion is below standard must to carry out secondary filter, should be sent to after each item index is qualified in the concentration make-up tank it is advanced the copper-bath concentration that strength of solution is allocated to be needed to production technique, uses in order to production system.
The invention has the advantages that: through the processing of above step; The production main technique that can realize real core gas shield welding wire fully is with copper-bath self-circulation utilization; Having reduced production cost, eliminated the pollution of cupric ion (heavy metal) to environment, is a project of benefiting the nation and the people; The present invention is oxidizing reaction temperature low (the atmospheric oxidation agent is >=90 ℃, and the present invention is 60-70 ℃) than air as the characteristics of oxygenant, energy consumption low (since the air blowing meeting a large amount of take away heat, keep temperature >=90 ℃ of reaction, need a large amount of additional heat).Deironing rate wherein of the present invention is up to 90%, and the atmospheric oxidation agent is 40～70%, so energy consumption is lower.
Description of drawings
Fig. 1 is this process flow diagram.
Embodiment
Below in conjunction with accompanying drawing the present invention is made detailed description:
The present invention is heated to 60-70 ℃ with waste liquid earlier, adds CaCO3, is transferred to 2-3 to the solution pH value, adds Na 2SO 4, carried out mechanical stirring 2 hours, owing to added CaCO 3Make its jelly and Ca ++Ion mixes and is floss, be convenient to filter, and the deironing rate can reach 90%.
The present invention is oxidizing reaction temperature low (the atmospheric oxidation agent is >=90 ℃, and the present invention is 60-70 ℃) than air as the characteristics of oxygenant, energy consumption low (since the air blowing meeting a large amount of take away heat, keep temperature >=90 ℃ of reaction, need a large amount of additional heat).Deironing rate wherein of the present invention is up to 90%, and the atmospheric oxidation agent is 40～70%, and concrete operations are following:
Embodiment 1:
(1): collect in the waste liquid deposit groove bluestone waste that discharges in the production system subsequent use;
(2): the bluestone waste suction that waste liquid is laid in the groove removes Fe ++In the groove,
(3): will be except that Fe ++Waste liquid heats in the groove, and Heating temperature is 60 ℃, and next adds CaCO 3Make the solution pH value transfer to 2, removing Fe then ++Add ydrogen peroxide 50 in the groove, through ydrogen peroxide 50 with Fe ++Be converted into Fe +++, add Na 2SO 4, carry out mechanical stirring and it was fully reacted in 1 hour, make it generate yellow ferrovanadium,
(4): yellow ferrovanadium in the step 3 is filtered removing, and copper-bath after filtering enters into each item index that liquid storage groove waits to chemically examine copper-bath,
(5): copper sulfate each item index of inspection chemical examination liquid storage groove, like Fe ++Below standard must returning to removed Fe ++Carry out secondary treatment in the groove, work as Fe ++(be FeSO 4During)>=10g/L, judge Fe ++Below standard, like Fe +++Below standard (the Fe of ion +++During>=0.1g/L, judge below standard) must carry out secondary filter, should be sent to after each item index is qualified in the concentration make-up tank it is advanced the copper-bath concentration that strength of solution is allocated to be needed to production technique, use in order to production system.
Embodiment 2:
(1): collect in the waste liquid deposit groove bluestone waste that discharges in the production system subsequent use;
(2): the bluestone waste suction that waste liquid is laid in the groove removes Fe ++In the groove,
(3): will be except that Fe ++Waste liquid heats in the groove, and Heating temperature is 70 ℃, and next adds CaCO 3Make the solution pH value transfer to 3, removing Fe then ++Add ydrogen peroxide 50 in the groove, through ydrogen peroxide 50 with Fe ++Be converted into Fe +++, add Na 2SO 4, carry out mechanical stirring and it was fully reacted in 1.5 hours, make it generate yellow ferrovanadium,
(4): with yellow ferrovanadium in the step 3, filter and remove, copper-bath after filtering enters into each item index that liquid storage groove waits to chemically examine copper-bath,
(5): copper sulfate each item index of inspection chemical examination liquid storage groove, like Fe ++Below standard must returning to removed Fe ++Carry out secondary treatment in the groove, work as Fe ++(be FeSO 4During)>=10g/L, judge Fe ++Below standard, like Fe +++Below standard (the Fe of ion +++During>=0.1g/L, judge below standard) must carry out secondary filter, should be sent to after each item index is qualified in the concentration make-up tank it is advanced the copper-bath concentration that strength of solution is allocated to be needed to production technique, use in order to production system.
Embodiment 3:
(1): collect in the waste liquid deposit groove bluestone waste that discharges in the production system subsequent use;
(2): the bluestone waste suction that waste liquid is laid in the groove removes Fe ++In the groove,
(3): will be except that Fe ++Waste liquid heats in the groove, and Heating temperature is 60 ℃, and next adds CaCO 3Make the solution pH value transfer to 2, removing Fe then ++Add ydrogen peroxide 50 in the groove, through ydrogen peroxide 50 with Fe ++Be converted into Fe +++, add Na 2SO 4, carry out mechanical stirring and it was fully reacted in 2 hours, make it generate yellow ferrovanadium,
(4): yellow ferrovanadium in the step 3 is filtered removing, and copper-bath after filtering enters into each item index that liquid storage groove waits to chemically examine copper-bath,
(5): copper sulfate each item index of inspection chemical examination liquid storage groove, like Fe ++Below standard must returning to removed Fe ++Carry out secondary treatment in the groove, work as Fe ++(be FeSO 4During)>=10g/L, judge Fe ++Below standard, like Fe +++Below standard (the Fe of ion +++During>=0.1g/L, judge below standard) must carry out secondary filter, should be sent to after each item index is qualified in the concentration make-up tank it is advanced the copper-bath concentration that strength of solution is allocated to be needed to production technique, use in order to production system.
Embodiment 4:
(1): the bluestone waste that discharges in the production system is collected in the waste liquid deposit groove, subsequent use.
(2): the bluestone waste suction that waste liquid is laid in the groove removes Fe ++In the groove,
(3): will be except that Fe ++Waste liquid heats in the groove, and Heating temperature is 70 ℃, and next adds CaCO 3Make the solution pH value transfer to 3, removing Fe then ++Add ydrogen peroxide 50 in the groove, through ydrogen peroxide 50 with Fe ++Be converted into Fe +++, add Na 2SO 4, carry out mechanical stirring and it was fully reacted in 2 hours, make it generate yellow ferrovanadium,
(4): yellow ferrovanadium in the step 3 is filtered removing, and copper-bath after filtering enters into each item index that liquid storage groove waits to chemically examine copper-bath,
(5): copper sulfate each item index of inspection chemical examination liquid storage groove, like Fe ++Below standard must returning to removed Fe ++Carry out secondary treatment in the groove, work as Fe ++(be FeSO 4During)>=10g/L, judge Fe ++Below standard, like Fe +++Below standard (the Fe of ion +++During>=0.1g/L, judge below standard) must carry out secondary filter, should be sent to after each item index is qualified in the concentration make-up tank it is advanced the copper-bath concentration that strength of solution is allocated to be needed to production technique, use in order to production system.
Embodiment 5:
(1): collect in the waste liquid deposit groove bluestone waste that discharges in the production system subsequent use;
(2): the bluestone waste suction that waste liquid is laid in the groove removes Fe ++In the groove,
(3): will be except that Fe ++Waste liquid heats in the groove, and Heating temperature is 65 ℃, and next adds CaCO 3Make the solution pH value transfer to 2.5, removing Fe then ++Add ydrogen peroxide 50 in the groove, through ydrogen peroxide 50 with Fe ++Be converted into Fe +++, add Na 2SO 4, carry out mechanical stirring and it was fully reacted in 2 hours, make it generate yellow ferrovanadium,
(4): yellow ferrovanadium in the step 3 is filtered removing, and copper-bath after filtering enters into each item index that liquid storage groove waits to chemically examine copper-bath,
(5): copper sulfate each item index of inspection chemical examination liquid storage groove, like Fe ++Below standard must returning to removed Fe ++Carry out secondary treatment in the groove, work as Fe ++(be FeSO 4During)>=10g/L, judge Fe ++Below standard, like Fe +++Below standard (the Fe of ion +++During>=0.1g/L, judge below standard) must carry out secondary filter, should be sent to after each item index is qualified in the concentration make-up tank it is advanced the copper-bath concentration that strength of solution is allocated to be needed to production technique, use in order to production system.

Claims (1)

1. the recoverying and utilizing method of a Chemical Copper Plating Effluent is characterized in that:
(1): collect in the waste liquid deposit groove bluestone waste that discharges in the production system subsequent use;
(2): the bluestone waste suction that waste liquid is laid in the groove removes Fe ++In the groove;
(3): will be except that Fe ++Waste liquid heats in the groove, and Heating temperature is 60～70 ℃, and next adds CaCO 3Make the solution pH value transfer to 2～3, removing Fe then ++Add ydrogen peroxide 50 in the groove, through ydrogen peroxide 50 with Fe ++Be converted into Fe +++, add Na 2SO 4, carry out mechanical stirring and it was fully reacted in 1～2 hour, make it generate yellow ferrovanadium;
(4): yellow ferrovanadium in the step 3 is filtered removing, and copper-bath after filtering enters into each item index that liquid storage groove waits to chemically examine copper-bath;
(5): copper sulfate each item index of inspection chemical examination liquid storage groove, like Fe ++Below standard must returning to removed Fe ++Carry out secondary treatment in the groove, like Fe +++Ion is below standard must to carry out secondary filter, should be sent to after each item index is qualified in the concentration make-up tank it is advanced the copper-bath concentration that strength of solution is allocated to be needed to production technique, uses in order to production system.
CN2011103011199A 2011-10-09 2011-10-09 Recycling method of chemical copper plating waste liquid Pending CN102503009A (en)

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Application Number Priority Date Filing Date Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948356A (en) * 2016-06-17 2016-09-21 大同新成新材料股份有限公司 Recycling method of washing waste liquid produced in chemical copper plating process
CN114031212A (en) * 2021-11-10 2022-02-11 江苏兴达钢帘线股份有限公司 Method and system for recycling waste copper sulfate plating solution

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4428840A (en) * 1982-06-16 1984-01-31 Homestake Mining Company Anionic and cationic removal of copper from cyanide-containing wastewater
CN1041339A (en) * 1988-09-22 1990-04-18 天钢钢研所 Oxidation method for reclaiming waste liquor of copper sulfate
CN1120591A (en) * 1994-10-13 1996-04-17 郑光 Method for prepn. of zinc oxide from zinc containing material
CN1827802A (en) * 2006-03-24 2006-09-06 浙江工业大学 Method for recovering valuable metals from electroplating sludge
CN101376521A (en) * 2008-09-24 2009-03-04 上海大学 Method for removing high concentration iron impurity in copper-contained sludge copper sulfate leaching liquid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4428840A (en) * 1982-06-16 1984-01-31 Homestake Mining Company Anionic and cationic removal of copper from cyanide-containing wastewater
CN1041339A (en) * 1988-09-22 1990-04-18 天钢钢研所 Oxidation method for reclaiming waste liquor of copper sulfate
CN1120591A (en) * 1994-10-13 1996-04-17 郑光 Method for prepn. of zinc oxide from zinc containing material
CN1827802A (en) * 2006-03-24 2006-09-06 浙江工业大学 Method for recovering valuable metals from electroplating sludge
CN101376521A (en) * 2008-09-24 2009-03-04 上海大学 Method for removing high concentration iron impurity in copper-contained sludge copper sulfate leaching liquid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948356A (en) * 2016-06-17 2016-09-21 大同新成新材料股份有限公司 Recycling method of washing waste liquid produced in chemical copper plating process
CN114031212A (en) * 2021-11-10 2022-02-11 江苏兴达钢帘线股份有限公司 Method and system for recycling waste copper sulfate plating solution

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Application publication date: 20120620