CN114230083A - Method for online recycling of copper plating waste liquid in surface treatment of metal product - Google Patents
Method for online recycling of copper plating waste liquid in surface treatment of metal product Download PDFInfo
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- CN114230083A CN114230083A CN202111637921.5A CN202111637921A CN114230083A CN 114230083 A CN114230083 A CN 114230083A CN 202111637921 A CN202111637921 A CN 202111637921A CN 114230083 A CN114230083 A CN 114230083A
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- 238000007747 plating Methods 0.000 title claims abstract description 324
- 239000010949 copper Substances 0.000 title claims abstract description 321
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 316
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 316
- 239000007788 liquid Substances 0.000 title claims abstract description 296
- 239000002699 waste material Substances 0.000 title claims abstract description 212
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 238000004381 surface treatment Methods 0.000 title claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 230000008025 crystallization Effects 0.000 claims abstract description 31
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 27
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 22
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 21
- 239000011790 ferrous sulphate Substances 0.000 claims description 21
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 238000001514 detection method Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002826 coolant Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002918 waste heat Substances 0.000 claims description 8
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 5
- 238000005192 partition Methods 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 173
- 239000000047 product Substances 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 230000008569 process Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000010802 sludge Substances 0.000 description 9
- 230000005484 gravity Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1617—Purification and regeneration of coating baths
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F2001/5218—Crystallization
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides a method for recycling copper plating waste liquid in metal product surface treatment on line. Mainly adopts MVR integrated technology (comprising a waste liquid heater, a waste liquid separator, a vapor compressor and a forced circulation pump) and utilizes CuSO in copper sulfate waste liquid4And FeSO4The solubility in the waste liquid has larger difference along with the change of temperature, and FeSO in the waste liquid is caused by the effect of temperature reduction and crystallization4Forming crystals, and centrifuging to separate FeSO4And separating copper sulfate waste liquid from the crystals, and returning the remaining copper sulfate waste liquid to the copper plating tank for continuous use. In order to realize linkage with copper plating production, a plurality of salinity meters and thermometers are arranged in the systemAnd the pressure transmitter is used for realizing the matching of the processing scale of the MVR evaporative crystallization system and the yield scale of a copper plating production line according to the set numerical value of the instrument, and ensuring the continuous and stable operation of the MVR evaporative crystallization system.
Description
Technical Field
The invention belongs to the technical field of environmental protection waste liquid treatment, and relates to a method for recycling copper plating waste liquid discharged by surface treatment of metal products, in particular to a method for recycling waste liquid generated by chemical copper plating on the surfaces of the metal products.
Background
In the process of transportation, storage and use of metal products, the existence of water vapor in the air can corrode the surface of the metal products, particularly, the corrosion is serious under the conditions of long-term storage and very high humidity in the air, the appearance of the metal products is influenced slightly, and the physical and chemical indexes such as mechanical strength and the like of the metal products are directly influenced seriously. Electroless copper plating is a process of depositing metal copper with a certain thickness and function on the surface of a substrate with catalytic activity through a displacement reaction or a reduction reaction under an acidic condition (pH = 1-2) or an alkaline condition (neutral or weakly alkaline, namely pH = 8.5-13.0). For metal articles, displacement electroless copper plating is a chemical reaction in which copper displaces iron after the metal article is subjected to corrosion activation. The pretreatment quality and the catalytic effect of the surface of the metal product are prerequisites for ensuring the smooth proceeding of the electroless copper plating and the quality of a copper layer. The copper plating waste liquid generally contains copper salt, acid plating agent, complexing agent, inhibitor and the like, wherein the copper salt in the copper plating liquid of the metal product is generally copper sulfate, the acid plating agent is sulfuric acid, the complexing agent adopts sodium tartrate, and the inhibitor adopts thiourea. The reaction principle is displacement chemical copper plating, which is a chemical reaction of copper to displace iron after a metal product is subjected to corrosion activation. The displacement reaction of the metal product in the acidic copper sulfate solution is generally as follows:
and (3) anode reaction:
in the electroplatingIn the process, in the process that Cu is continuously plated on the surface of the metal product, Cu in copper sulfate in the plating solution in the chemical plating bath2+Will be consumed continuously, and at the same time, the Fe on the surface of the metal product is replaced and enters into the plating solution, and forms ferrous sulfate with the sulfate in the plating solution. The mass concentration of ferrous sulfate in the solution is not more than 150g/L, and ferrous ions with too high concentration can be crystallized on the surface of the steel wire and are not easy to remove, so that the replacement of copper ions is influenced, and the quality of a copper-plated layer is seriously deteriorated. Therefore, when Fe is contained in the copper plating solution2+When the concentration is increased to a certain value, the copper plating waste liquid must be replaced to ensure the process quality of the chemical copper plating of the metal products. When the copper plating solution is replaced, the general waste solution contains H2SO4About 50-100 g/L; FeSO4About 150-200 g/L, CuSO4: 50-120 g/L. Therefore, the chemical copper plating waste liquid has the characteristics of high concentration of heavy metal pollutants and high acidity.
The treatment of the traditional copper plating waste liquid mainly adopts two modes: one method is to combine with other wastewater of chemical copper plating wire and remove the wastewater by a traditional precipitation method, the traditional precipitation process has high requirements on reaction conditions and poor impact resistance, and the effluent quality is unstable when the raw water quantity, water quality and reaction conditions fluctuate greatly, so that the effect is difficult to ensure. In addition, a flocculating agent and a coagulant aid are required to be added into the wastewater to form a large amount of chemical sludge, so that the operation cost is increased. The other method is to adopt an adsorption method, a membrane method or an electrochemical reduction method to recover heavy metals, but the heavy metal recovery process has the disadvantages of high operation cost, strict process control requirement, and the intermittent discharge of copper plating waste liquid, which is very unfavorable for the actual operation of the heavy metal recovery process.
The inventor of the invention in the previous period adopts a multi-effect evaporation crystallization process to recover copper sulfate in an off-line mode, and finds the following problems in the use process:
the method has the advantages that copper sulfate is recycled in an off-line mode, a multi-effect evaporation system needs to be frequently heated up and cooled down, the system is complex to operate, and energy is wasted.
The multistage graphite heater and the evaporator are arranged in the system, the temperature is raised and lowered intermittently for a long time, the graphite block has the leakage problem due to frequent alternation of cold and heat, and the copper sulfate waste liquid has strong corrosion and certain potential safety hazard.
The system is intermittently used, is not tightly matched with a copper plating production line, and has the condition that the supply quantity of the copper plating solution is not matched with the production demand quantity.
The multi-effect evaporation system is complex in composition, and equipment in the system has many damaged risk points, so that the system is high in shutdown risk, and stable operation of the system is affected.
The multi-effect evaporation system adopts an intermittent operation mode, the fluctuation of the steam demand is large, and the steam supply rule of the copper plating production line is greatly influenced.
Disclosure of Invention
The invention aims to provide a set of on-line replacement and recovery technology suitable for copper plating waste liquid in the surface treatment process of metal products. According to Fe in the copper plating solution2+Has a crucial influence on the replacement chemical copper plating process, and a small amount of Fe2+The speed of the displacement reaction on the metal surface can be effectively inhibited, so that the tendency of coarse copper layer grains and crisp copper layer caused by too high displacement speed is reduced; when Fe2+When the concentration is too high, not only the rate of the metal product avoiding the replacement reaction is remarkably decreased, but also iron salt crystallized in the plating solution is deposited on the surface of the steel wire, thereby seriously deteriorating the quality of the copper-plated layer. Thus Fe in the copper plating bath2+The concentration being in a dynamic equilibrium of the concentration, Fe2+The smaller the variation range of the concentration, the better the copper plating quality of the metal product.
For realizing Fe in copper plating solution of metal products2+The concentration dynamic balance is realized by adopting an MVR integrated technology (comprising a waste liquid heater, a waste liquid separator, a vapor compressor and a forced circulation pump) and utilizing CuSO in the copper sulfate waste liquid4And FeSO4The solubility in the waste liquid has larger difference along with the change of temperature, and FeSO in the waste liquid is caused by the effect of temperature reduction and crystallization4Forming crystals, and centrifuging to separate FeSO4And separating copper sulfate waste liquid from the crystals, and returning the remaining copper sulfate waste liquid to the copper plating tank for continuous use.
Therefore, the invention discloses an online recycling method of copper plating waste liquid in surface treatment of metal products, which is characterized by comprising the following steps:
firstly, a waste liquid buffer tank:
the copper sulfate plating solution automatically flows into a waste liquid buffer tank through a liquid discharge pipe arranged on a copper plating tank, and then the copper plating solution is lifted into a waste liquid preheater through a lifting pump in the buffer tank; the in-tank online salinity meter is arranged to detect the density of the copper plating solution, and the scale of the copper plating solution entering a subsequent MVR system is determined according to the density change of the copper plating solution so as to ensure Fe in the copper plating solution in the copper plating tank2+The concentration is changed between 80 and 100g/L, so that the quality of a coating of a metal product is ensured;
the waste liquid preheater is provided with:
the copper plating waste liquid contains 80g/L sulfuric acid liquid, waste heat steam after heat exchange of a graphite preheater is discharged out of the system through a condenser, the preheated copper plating liquid enters a waste liquid evaporator to be concentrated, temperature on-line detection is arranged at a copper plating liquid outlet of the waste liquid preheater, and the temperature of the copper plating liquid at the outlet participates in variable frequency control of a steam compressor;
heater for waste liquid of the third step
The preheated copper plating solution enters a waste liquid heater in a counter-flow manner, the content of ferrous sulfate in the copper plating solution is controlled to be 80-100g/L through evaporation, the inlet of the waste liquid heater is provided with temperature on-line detection, and the temperature is controlled to be 50-60 ℃ to control the variable frequency parameter of a steam compressor according to the feeding temperature; the shell side of the waste liquid heater is provided with a pressure detector, the pressure is controlled to be 0.14MPA, the pressure of steam in the waste liquid heater is detected, and the influence of non-condensable gas on the heat exchange effect is avoided;
fourth waste liquid separator
After the copper plating solution is heated by a waste liquid heater, carrying out gas-liquid separation, pressurizing and acting the generated steam by a steam compressor to generate high-pressure steam, then lifting the copper plating solution subjected to gas-liquid separation into the waste liquid heater by using a forced circulation pump to form internal circulation of the copper plating solution in the waste liquid heater and the waste liquid separator, and continuously heating the copper plating waste liquid; the temperature is controlled to be 112 ℃, a salinity meter is arranged in the waste liquid separator to detect the density of the copper plating solution and control the density to be 1.21g/cm3When being Fe2+After the concentration reaches the density requirementThe copper plating solution is discharged into a cooling crystallization tank through the control of an electric valve at a discharge port;
step-five cooling crystallization tank
Controlling the operation in a cooling crystallizer in a heat exchange mode with a coolant partition wall, reducing the temperature of mother liquor, detecting the temperature in a tank, discharging when the temperature is reduced to 70 ℃ which is set by a system, discharging mixed crystal slurry into a centrifugal machine, and carrying out solid-liquid separation; the coolant refers to circulating water;
sixthly, a centrifuge
Separating the crystal from the mother liquor by a centrifugal machine; collecting the formed ferrous sulfate crystals, feeding the mother liquor discharged by a centrifugal machine into a feed liquor collecting tank, and regulating CuSO4After the concentration, the mixture enters a production line for continuous use;
feed liquid collecting tank
A feed liquid collecting tank, wherein the interior of the tank is divided into two independent areas, namely a copper plating solution preparation area and a copper plating solution using area; a salinity meter is arranged in the copper plating solution preparation area, the copper plating solution treated by a centrifuge firstly enters the preparation area, and CuSO with the concentration of 200g/L is added into the copper plating solution according to the density value of the copper plating solution4Solution until the density value of the copper plating solution reaches the specified value of 1.15g/cm3And lifting the prepared copper plating solution to a copper plating solution using area through an overflow pump, and finally supplementing the prepared copper plating solution into the copper plating tank according to the liquid level of the copper plating tank.
The invention further discloses an application of the online recycling method of the copper plating waste liquid in the surface treatment of the metal product in reducing the using amount of the chemical copper plating waste liquid; the experimental results show that: fe in copper plating solution is crystallized through MVR evaporation2+After the concentration is reduced to 70g/L, the chemical copper plating solution is recycled. The conventional use of electroless copper plating solution is Fe in the copper plating bath2+And after the concentration reaches 120g/L, completely discharging the waste copper plating solution out and replacing the copper plating solution, and treating the discharged waste copper plating solution by a chemical precipitation method. The patent refers to the field of 'chemical mechanical polishing of copper surfaces to remove iron therefrom'2+After the concentration is reduced to 70g/L, the waste caused by the discharge of the waste copper plating solution is avoided.
The invention is described in more detail below:
a method for recycling copper plating waste liquid on line in surface treatment of metal products comprises the following steps:
first waste liquid buffer tank
Copper sulfate plating solution in a copper plating tank in a surface treatment production line continuously enters a waste liquid buffer tank to provide buffer for the copper sulfate plating solution to enter an MVR system, the copper sulfate plating solution automatically flows into the waste liquid buffer tank through a liquid discharge pipe arranged on the copper plating tank under the action of gravity, and then the copper plating solution is lifted to a waste liquid preheater through a lifting pump in the buffer tank. The in-tank online salinity meter is arranged to detect the density of the copper plating solution, and the scale of the copper plating solution entering a subsequent MVR system is determined according to the density change of the copper plating solution so as to ensure Fe in the copper plating solution in the copper plating tank2+The concentration is changed between 80 and 100g/L, and the quality of the coating of the metal product is ensured.
Waste liquid preheater
The copper plating solution is lifted to a waste liquid preheater after passing through a waste liquid buffer tank, and waste heat steam generated by a subsequent process is utilized to preheat copper plating waste entering a system, so that the energy consumption of the system is reduced. The copper plating waste liquid contains 80g/L sulfuric acid liquid, and the material of the overflowing part of the preheater needs to be made of corrosion-resistant graphite. And the waste heat steam after heat exchange is discharged out of the system through a condenser. And (4) feeding the preheated copper plating solution into a waste liquid evaporator for waste liquid concentration. And a copper plating solution outlet of the waste liquid preheater is provided with temperature on-line detection, and participates in the variable frequency control of the steam compressor according to the temperature of the outlet copper plating solution.
Heater for waste liquid of the third step
The preheated copper plating solution enters a waste liquid heater in a counter-flow mode. After the copper plating solution enters the waste liquid heater, the ferrous sulfate content in the copper plating solution is increased to the concentration of cooling crystallization through the evaporation and concentration effect, and simultaneously, the concentration of copper sulfate in the waste liquid can be ensured to form crystallization at least. The heating source comes from the compression work of the steam compressor on the steam produced by the subsequent waste liquid separator. The waste liquid heater is a tubular heater, and a corrosion-resistant graphite material is required because the copper plating solution is strong acid. Waste heat steam generated by the waste liquid heater reversely flows into the waste liquid preheater to preheat the copper plating liquid, so that energy consumption is reduced. And the inlet of the waste liquid heater is provided with temperature on-line detection, and the variable frequency parameter of the steam compressor is controlled according to the feeding temperature. The waste liquid heater is provided with pressure detection to ensure that the pressure in the waste liquid heater is in a stable state and transmits an alarm signal when the pressure exceeds the system pressure.
Fourth waste liquid separator
After the copper plating liquid is heated by the waste liquid heater, gas-liquid separation is needed to achieve the purpose of concentrating the copper plating liquid, the generated steam is pressurized by the steam compressor to do work to generate high-pressure steam, then the copper plating liquid subjected to gas-liquid separation is lifted by the forced circulation pump to enter the waste liquid heater, internal circulation of the copper plating liquid in the waste liquid heater and the waste liquid separator is formed, and the copper plating waste liquid is continuously heated. The forced circulation pump adopts frequency conversion control, and the frequency range is adjusted according to the salinity meter in the waste liquid buffer tank. A salinity meter is arranged in the waste liquid separator to detect the density of the copper plating liquid when Fe2+After the concentration meets the requirement of the dynamic discharge parameters, the copper plating solution is discharged into a cooling crystallization tank through the control of an electric valve at a discharge port.
Step-five cooling crystallization tank
And circularly heating the copper plating solution through a waste liquid heater and a waste liquid separator to reach the crystallization concentration of ferrous sulfate, and then cooling and crystallizing in a cooling crystallization tank. By utilizing the characteristic that the solubility of the ferrous sulfate is reduced along with the reduction of the temperature, the operation temperature in the cooling crystallizer is controlled according to different crystallization temperatures of the ferrous sulfate and the copper sulfate and through a mode of heat exchange with the dividing wall of the coolant, the temperature of the mother liquor is reduced, most of the ferrous sulfate in the waste liquid is ensured to be crystallized and separated out, and only a small part of the copper sulfate is separated out. And detecting the temperature in the tank, and discharging when the temperature is reduced to the set temperature of the system. Discharging the mixed crystal slurry into a centrifuge for solid-liquid separation.
Sixthly, a centrifuge
After cooling crystallization, the formed crystal slurry enters a centrifuge, and crystals in the crystal slurry discharged from the cooling crystallizer are separated from mother liquor through the separation effect of the centrifuge. Collecting the formed ferrous sulfate crystals, feeding the mother liquor discharged by a centrifugal machine into a feed liquor collecting tank, and regulating CuSO4After concentration, the mixture enters a production line for continuous use.
Feed liquid collecting tank
Through solid-liquid separationAnd discharging the copper plating solution into a feed solution collecting tank, wherein the tank is divided into two independent areas, namely a copper plating solution preparation area and a copper plating solution using area. A salinity meter is arranged in the copper plating solution preparation area, the copper plating solution treated by a centrifuge firstly enters the preparation area, and CuSO with the concentration of 200g/L is added into the copper plating solution according to the density value of the copper plating solution4And (4) solution, namely, lifting the prepared copper plating solution to a copper plating solution using area through an overflow pump until the density value of the copper plating solution reaches the specified parameter, and finally supplementing the prepared copper plating solution into the copper plating tank according to the liquid level of the copper plating tank.
The invention discloses a method for recycling copper plating waste liquid on line in the surface treatment of metal products, which has the technical characteristics and effects that:
the invention solves the problems that the traditional physical and chemical treatment method for the copper plating waste liquid has high treatment cost and low treatment efficiency and sludge is a dangerous waste, changes the treatment direction of the copper plating liquid, recycles the copper plating liquid and saves the production cost of copper plating production. Compared with the common off-line evaporation crystallization process of the copper plating solution, the invention combines with the copper plating production line to form linkage, and detects Fe in the copper plating solution through the detection of an on-line instrument2+Concentration, continuously treating the copper plating solution in the copper plating tank, and adjusting the feeding amount of the MVR evaporative crystallization system according to the detection result to adapt to the production load change of a copper plating production line, thereby realizing Fe in the copper plating solution2+The concentration presents a dynamic equilibrium of concentrations. The problems that the off-line evaporative crystallization process needs to intermittently process the copper plating solution, the power is frequently turned on and off and the energy consumption is overlarge are solved, and the problem of complex operation caused by frequent starting of the system is also solved.
In order to realize linkage with copper plating production, a plurality of salinity meters, thermometers and pressure transmitters are arranged in the system, the processing scale of the MVR evaporative crystallization system is matched with the output scale of the copper plating production line according to the set numerical value of the instruments, and the continuous and stable operation of the MVR evaporative crystallization system is ensured.
Drawings
FIG. 1 is a schematic flow chart of the online recycling method of copper plating waste liquid in the surface treatment of metal products;
FIG. 2 is a process flow diagram of a chemical precipitation treatment.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The raw materials and reagents used in the present invention are commercially available. In order to explain the implementation method of the invention more fully, an implementation example of the method for treating and recycling the electroless copper plating waste liquid in the steel industry is provided. These examples are merely illustrative and do not limit the scope of the invention.
Example 1
A method for recycling copper plating waste liquid on line in the surface treatment of metal products comprises the following steps:
firstly, a waste liquid buffer tank:
the copper sulfate plating solution automatically flows into a waste liquid buffer tank through a liquid discharge pipe arranged on a copper plating tank, and then the copper plating solution is lifted into a waste liquid preheater through a lifting pump in the buffer tank; the in-tank online salinity meter is arranged to detect the density of the copper plating solution, and the scale of the copper plating solution entering a subsequent MVR system is determined according to the density change of the copper plating solution so as to ensure Fe in the copper plating solution in the copper plating tank2+The concentration is changed at 80g/L, so that the quality of a coating of a metal product is ensured;
the waste liquid preheater is provided with:
the copper plating waste liquid contains 80g/L sulfuric acid liquid, waste heat steam after heat exchange of a graphite preheater is discharged out of the system through a condenser, the preheated copper plating liquid enters a waste liquid evaporator to be concentrated, temperature on-line detection is arranged at a copper plating liquid outlet of the waste liquid preheater, and the temperature of the copper plating liquid at the outlet participates in variable frequency control of a steam compressor;
heater for waste liquid of the third step
The preheated copper plating solution enters a waste liquid heater in a counter-flow manner, the content of ferrous sulfate in the copper plating solution is controlled to be 80g/L through evaporation, the inlet of the waste liquid heater is provided with temperature on-line detection, and the temperature is controlled to be 50 ℃ to control the variable frequency parameter of a steam compressor according to the feeding temperature; the shell side of the waste liquid heater is provided with a pressure detector, the pressure is controlled to be 0.14MPA, the pressure of steam in the waste liquid heater is detected, and the influence of non-condensable gas on the heat exchange effect is avoided;
fourth waste liquid separator
After the copper plating solution is heated by a waste liquid heater, carrying out gas-liquid separation, pressurizing and acting the generated steam by a steam compressor to generate high-pressure steam, then lifting the copper plating solution subjected to gas-liquid separation into the waste liquid heater by using a forced circulation pump to form internal circulation of the copper plating solution in the waste liquid heater and the waste liquid separator, and continuously heating the copper plating waste liquid; the temperature is controlled to be 112 ℃, a salinity meter is arranged in the waste liquid separator to detect the density of the copper plating solution and control the density to be 1.21g/cm3When being Fe2+After the concentration meets the density requirement, discharging the copper plating solution into a cooling crystallization tank through the control of an electric valve at a discharge port;
step-five cooling crystallization tank
Controlling the operation in a cooling crystallizer in a heat exchange mode with a coolant partition wall, reducing the temperature of mother liquor, detecting the temperature in a tank, discharging when the temperature is reduced to 70 ℃ which is set by a system, discharging mixed crystal slurry into a centrifugal machine, and carrying out solid-liquid separation; the coolant refers to circulating water;
sixthly, a centrifuge
Separating the crystal from the mother liquor by a centrifugal machine; collecting the formed ferrous sulfate crystals, feeding the mother liquor discharged by a centrifugal machine into a feed liquor collecting tank, and regulating CuSO4After the concentration, the mixture enters a production line for continuous use;
feed liquid collecting tank
A feed liquid collecting tank, wherein the interior of the tank is divided into two independent areas, namely a copper plating solution preparation area and a copper plating solution using area; a salinity meter is arranged in the copper plating solution preparation area, the copper plating solution treated by a centrifuge firstly enters the preparation area, and CuSO with the concentration of 200g/L is added into the copper plating solution according to the density value of the copper plating solution4Solution to copper plating solutionThe density value reaches the specified value of 1.15g/cm3And lifting the prepared copper plating solution to a copper plating solution using area through an overflow pump, and finally supplementing the prepared copper plating solution into the copper plating tank according to the liquid level of the copper plating tank.
Example 2
A method for recycling copper plating waste liquid on line in the surface treatment of metal products comprises the following steps:
firstly, a waste liquid buffer tank:
the copper sulfate plating solution automatically flows into a waste liquid buffer tank through a liquid discharge pipe arranged on a copper plating tank, and then the copper plating solution is lifted into a waste liquid preheater through a lifting pump in the buffer tank; the in-tank online salinity meter is arranged to detect the density of the copper plating solution, and the scale of the copper plating solution entering a subsequent MVR system is determined according to the density change of the copper plating solution so as to ensure Fe in the copper plating solution in the copper plating tank2+The concentration is changed at 100g/L, so that the quality of a coating of a metal product is ensured;
the waste liquid preheater is provided with:
the copper plating waste liquid contains 80g/L sulfuric acid liquid, waste heat steam after heat exchange of a graphite preheater is discharged out of the system through a condenser, the preheated copper plating liquid enters a waste liquid evaporator to be concentrated, temperature on-line detection is arranged at a copper plating liquid outlet of the waste liquid preheater, and the temperature of the copper plating liquid at the outlet participates in variable frequency control of a steam compressor;
heater for waste liquid of the third step
The preheated copper plating solution enters a waste liquid heater in a counter-flow manner, the content of ferrous sulfate in the copper plating solution is controlled to be 80-100g/L through evaporation, the inlet of the waste liquid heater is provided with temperature on-line detection, and the temperature is controlled to be 60 ℃ to control the variable frequency parameter of a steam compressor according to the feeding temperature; the shell side of the waste liquid heater is provided with a pressure detector, the pressure is controlled to be 0.14MPA, the pressure of steam in the waste liquid heater is detected, and the influence of non-condensable gas on the heat exchange effect is avoided;
fourth waste liquid separator
The copper plating solution is heated by a waste liquid heater and then is subjected to gas-liquid separation, the generated steam is pressurized by a steam compressor to do work to generate high-pressure steam, and then the copper plating solution subjected to gas-liquid separation is lifted by a forced circulation pump to enterThe waste liquid heater is used for forming the internal circulation of the copper plating liquid in the waste liquid heater and the waste liquid separator and continuously heating the copper plating waste liquid; the temperature is controlled to be 112 ℃, a salinity meter is arranged in the waste liquid separator to detect the density of the copper plating solution and control the density to be 1.21g/cm3When being Fe2+After the concentration meets the density requirement, discharging the copper plating solution into a cooling crystallization tank through the control of an electric valve at a discharge port;
step-five cooling crystallization tank
Controlling the operation in a cooling crystallizer in a heat exchange mode with a coolant partition wall, reducing the temperature of mother liquor, detecting the temperature in a tank, discharging when the temperature is reduced to 70 ℃ which is set by a system, discharging mixed crystal slurry into a centrifugal machine, and carrying out solid-liquid separation; the coolant refers to circulating water;
sixthly, a centrifuge
Separating the crystal from the mother liquor by a centrifugal machine; collecting the formed ferrous sulfate crystals, feeding the mother liquor discharged by a centrifugal machine into a feed liquor collecting tank, and regulating CuSO4After the concentration, the mixture enters a production line for continuous use;
feed liquid collecting tank
A feed liquid collecting tank, wherein the interior of the tank is divided into two independent areas, namely a copper plating solution preparation area and a copper plating solution using area; a salinity meter is arranged in the copper plating solution preparation area, the copper plating solution treated by a centrifuge firstly enters the preparation area, and CuSO with the concentration of 200g/L is added into the copper plating solution according to the density value of the copper plating solution4Solution until the density value of the copper plating solution reaches the specified value of 1.15g/cm3And lifting the prepared copper plating solution to a copper plating solution using area through an overflow pump, and finally supplementing the prepared copper plating solution into the copper plating tank according to the liquid level of the copper plating tank.
Example 3
A method for recycling copper plating waste liquid on line in the surface treatment of metal products comprises the following steps:
firstly, a waste liquid buffer tank:
under the action of gravity, the copper sulfate plating solution automatically flows into a waste liquid buffer tank through a liquid discharge pipe arranged on a copper plating tank, and then the copper plating solution is lifted into a waste liquid preheater through a lifting pump in the buffer tank; in-tank on-line salinity meter for detecting copper plating liquidDensity, determining the scale of the copper plating solution entering a subsequent MVR system according to the density change of the copper plating solution so as to ensure Fe in the copper plating solution in the copper plating tank2+The concentration is changed at 80g/L, so that the quality of a coating of a metal product is ensured;
the waste liquid preheater is provided with:
the copper plating waste liquid contains 80g/L sulfuric acid liquid, the material of the overflowing part of the preheater is made of corrosion-resistant graphite, waste heat steam after heat exchange is discharged out of the system through a condenser, preheated copper plating liquid enters a waste liquid evaporator to carry out waste liquid concentration, a copper plating liquid outlet of the waste liquid preheater is provided with temperature on-line detection, and the temperature participates in the variable frequency control of the steam compressor according to the temperature of the copper plating liquid at the outlet;
heater for waste liquid of the third step
The preheated copper plating solution enters a waste liquid heater in a counter-flow manner, the content of ferrous sulfate in the copper plating solution is increased to the concentration of cooling crystallization through the evaporation concentration effect, the inlet of the waste liquid heater is provided with temperature on-line detection, and the variable frequency parameter of a steam compressor is controlled according to the feeding temperature; the waste liquid heater is provided with pressure detection to ensure that the pressure in the waste liquid heater is in a stable state and transmits an alarm signal when the pressure exceeds the system pressure;
fourth waste liquid separator
After the copper plating solution is heated by a waste liquid heater, gas-liquid separation is carried out to achieve the purpose of concentrating the copper plating solution, the generated steam is pressurized by a steam compressor to do work to generate high-pressure steam, then the copper plating solution subjected to gas-liquid separation is lifted by a forced circulation pump to enter the waste liquid heater, the copper plating solution is circulated in the waste liquid heater and a waste liquid separator, and the copper plating waste liquid is continuously heated; a salinity meter is arranged in the waste liquid separator to detect the density of the copper plating liquid when Fe2+After the concentration meets the requirement of the dynamic discharge parameters, discharging the copper plating solution into a cooling crystallization tank through the control of an electric valve at a discharge port;
step-five cooling crystallization tank
Controlling the operation temperature in the cooling crystallizer in a heat exchange mode with the dividing wall of the coolant, reducing the temperature of the mother liquor, and ensuring that most of ferrous sulfate in the waste liquid is crystallized and separated out, and only a small part of copper sulfate is separated out; and detecting the temperature in the tank, discharging when the temperature is reduced to the set temperature of the system, and discharging the mixed crystal slurry into a centrifugal machine for solid-liquid separation.
Sixthly, a centrifuge
After cooling crystallization, the formed crystal slurry enters a centrifugal machine, and crystals in the crystal slurry discharged from the cooling crystallizer are separated from mother liquor through the separation effect of the centrifugal machine; collecting the formed ferrous sulfate crystals, feeding the mother liquor discharged by a centrifugal machine into a feed liquor collecting tank, and regulating CuSO4After the concentration, the mixture enters a production line for continuous use;
feed liquid collecting tank
Discharging the copper plating solution subjected to solid-liquid separation into a feed solution collecting tank, wherein the tank is divided into two independent areas, namely a copper plating solution preparation area and a copper plating solution using area; a salinity meter is arranged in the copper plating solution preparation area, the copper plating solution treated by a centrifuge firstly enters the preparation area, and CuSO with the concentration of 200g/L is added into the copper plating solution according to the density value of the copper plating solution4And (4) solution, namely, lifting the prepared copper plating solution to a copper plating solution using area through an overflow pump until the density value of the copper plating solution reaches the specified parameter, and finally supplementing the prepared copper plating solution into the copper plating tank according to the liquid level of the copper plating tank.
Example 5
The chemical copper plating waste liquid treatment engineering of the welding material workshop of the metal product processing enterprise is selected, and the water quality of the chemical copper plating waste liquid is as follows:
the implementation process of the invention is explained in detail with the attached drawings:
firstly, a waste liquid buffer tank: copper plating solution produced by copper plating is lifted to a waste liquid buffer tank through a corrosion-resistant pump of the copper plating tank, the tank liquid level in the copper plating tank is adjusted, and the stable operation of an MVR evaporation crystallization system is ensured. The copper plating solution contains a large amount of H2SO4The effective volume of the buffer tank is 2m and the material of the glass fiber reinforced plastic needs to be selected for corrosion resistance3。
The waste liquid preheater is provided with: the copper plating solution is lifted to a waste liquid preheater by a corrosion-resistant pump and is heated with the waste liquidThe preheating discharged by the device carries out heat exchange, and the feeding temperature of the copper plating solution is improved. The waste liquid preheater adopts a tubular form, the graphite lining achieves the purpose of corrosion resistance, and the heat exchange area is 20m2。
The waste liquid heater: the preheated copper plating solution is mixed with the feed liquid circulating in the system through the inlet end of the forced circulation pump, and then enters the waste liquid heater. And the copper plating solution is heated by heat interaction with steam pressurized by a steam compressor to complete the heating process of the copper plating solution. The waste liquid heater adopts a tubular form, graphite is lined to achieve the purpose of corrosion resistance, and the heat exchange area is 30m2。
Fourth, a waste liquid separator: the heated copper plating solution enters a waste liquid separator through the lifting action of a forced circulation pump, saturated gas enters the waste liquid separator by utilizing different specific gravities of gas, liquid and solid, the liquid and the solid with large specific gravities are separated from the gas in an instant weightlessness mode, a vortex is formed by utilizing the flow velocity of outlet gas to enable the liquid and the solid with large specific gravities to be deposited on the lower portion of the separator, the separated gas flows out of the upper portion of the separator, enters a steam compressor and enters a waste liquid preheater as secondary steam under the pressure-price effect to continue heating the copper plating solution. The lower end of the waste liquid separator is provided with a copper plating liquid discharge port, a salinity meter is arranged in the waste liquid separator to detect the density of the copper plating liquid, and when Fe is generated2+After the concentration meets the requirement of the dynamic discharge parameters, the copper plating solution is discharged into a cooling crystallization tank through the control of an electric valve at a discharge port. The graphite lining of the waste liquid separator achieves the purpose of corrosion resistance, and the effective volume is 1m2。
Step five, cooling the crystallizing tank: the characteristic that the solubility of ferrous sulfate decreases along with the decrease of temperature is utilized, and the temperature of the mother liquor is reduced through the heat exchange with the wall of the coolant, so that crystals are separated out. Meanwhile, the cooling crystallization temperature is controlled, so that the minimum amount of copper sulfate in the copper plating waste liquid is ensured to be crystallized and separated out at the temperature, and the loss of effective copper plating liquid components is reduced.
Sixthly, a centrifuge: after the chemical copper plating waste liquid is cooled and crystallized, feed liquid containing ferrous sulfate crystals enters a centrifugal machine, and the crystals in crystal slurry discharged from a cooling crystallizer are separated from mother liquid. And (4) independently collecting crystals, and discharging residual mother liquor into a feed liquid collecting tank.
Feed liquid holding tank: the system finally adopts a feed liquid collecting tank for collecting feed liquid, the interior of the tank is divided into two independent areas, namely a copper plating solution preparation area and a copper plating solution using area, and the effective volume of the copper plating solution preparation area is 0.5m3Effective volume of copper plating solution using area is 2m3. A salinity meter is arranged in the copper plating solution preparation area, the copper plating solution treated by a centrifuge firstly enters the preparation area, and CuSO with the concentration of 200g/L is added into the copper plating solution according to the density value of the copper plating solution4The prepared copper plating solution is lifted to a copper plating solution using area through an overflow pump until the density value of the copper plating solution reaches the specified parameters, and finally the prepared copper plating solution is supplemented into the copper plating tank according to the liquid level of the copper plating tank.
The indexes of the electroless copper plating treated by the method are shown in the following table:
the operating cost of the project is shown as the following table:
the cost of preparing 1 ton of electroless copper plating solution is about 1900 yuan, and the cost of treating 1 ton of electroless copper plating waste solution by the online recovery system provided by the invention is 426.5 yuan. Therefore, the technology not only solves the treatment problem of the chemical copper plating waste liquid, but also provides a set of waste liquid recycling method different from the existing heavy metal recovery, reduces the operation components of enterprises, and has considerable economic benefit and huge environmental benefit.
Example 6
The traditional copper sulfate waste liquid treatment adopts a mode that waste liquid is mixed with other acidic waste water discharged by a production line and then treated by a chemical precipitation method, and the specific process flow is shown in figure 2:
the copper sulfate waste liquid is lifted to a coagulation reaction through a corrosion-resistant pump after the water quality and the water quantity are homogenized through a waste liquid adjusting tankShould be slotted. In a coagulation reaction tank, adding liquid caustic soda, sodium hypochlorite and a flocculating agent into the waste liquid, and adjusting the pH of the waste liquid to about 9 by the liquid caustic soda to obtain Cu in the waste liquid2+And Fe2+Conversion to Cu (OH)2And Fe (OH)2Precipitate, oxidation of Fe (OH) by sodium hypochlorite2Conversion to Fe (OH)3Finally Cu (OH) under the action of a flocculating agent2And Fe (OH)3Larger flocs are formed. The reacted copper plating solution flows into an inclined tube sedimentation tank through gravity, larger flocs formed by a coagulation reaction tank form precipitated sludge sediment and a bottom sludge hopper under the action of gravity, and supernatant enters a precision filter through an overflow weir for further solid-liquid separation, and finally reaches the standard to be discharged. The sludge in the sludge hopper at the bottom of the inclined tube sedimentation tank is lifted to a plate-and-frame filter press by a sludge pump for sludge treatment, and the finally formed sludge contains heavy metals and must be delivered to a hazardous waste disposal unit for safe disposal.
The emission index of the copper plating waste liquid is as follows:
taking 1 ton of copper plating waste liquid as an example, the cost for treating the copper plating waste liquid is calculated as shown in the following table:
Claims (2)
1. a method for on-line recycling of copper plating waste liquid in surface treatment of metal products is characterized by comprising the following steps:
firstly, a waste liquid buffer tank:
the copper sulfate plating solution automatically flows into a waste liquid buffer tank through a liquid discharge pipe arranged on a copper plating tank, and then the copper plating solution is lifted into a waste liquid preheater through a lifting pump in the buffer tank; the in-tank online salinity meter is arranged to detect the density of the copper plating solution, and the scale of the copper plating solution entering a subsequent MVR system is determined according to the density change of the copper plating solution so as to ensure the copper plating solution in the copper plating tankMiddle Fe2+The concentration is changed between 80 and 100g/L, so that the quality of a coating of a metal product is ensured;
the waste liquid preheater is provided with:
the copper plating waste liquid contains 80g/L sulfuric acid liquid, waste heat steam after heat exchange of a graphite preheater is discharged out of the system through a condenser, the preheated copper plating liquid enters a waste liquid evaporator to be concentrated, temperature on-line detection is arranged at a copper plating liquid outlet of the waste liquid preheater, and the temperature of the copper plating liquid at the outlet participates in variable frequency control of a steam compressor;
heater for waste liquid of the third step
The preheated copper plating solution enters a waste liquid heater in a counter-flow manner, the content of ferrous sulfate in the copper plating solution is controlled to be 80-100g/L through evaporation, the inlet of the waste liquid heater is provided with temperature on-line detection, and the temperature is controlled to be 50-60 ℃ to control the variable frequency parameter of a steam compressor according to the feeding temperature; the shell side of the waste liquid heater is provided with a pressure detector, the pressure is controlled to be 0.14MPA, the pressure of steam in the waste liquid heater is detected, and the influence of non-condensable gas on the heat exchange effect is avoided;
fourth waste liquid separator
After the copper plating solution is heated by a waste liquid heater, carrying out gas-liquid separation, pressurizing and acting the generated steam by a steam compressor to generate high-pressure steam, then lifting the copper plating solution subjected to gas-liquid separation into the waste liquid heater by using a forced circulation pump to form internal circulation of the copper plating solution in the waste liquid heater and the waste liquid separator, and continuously heating the copper plating waste liquid; the temperature is controlled to be 112 ℃, a salinity meter is arranged in the waste liquid separator to detect the density of the copper plating solution and control the density to be 1.21g/cm3When being Fe2+After the concentration meets the density requirement, discharging the copper plating solution into a cooling crystallization tank through the control of an electric valve at a discharge port;
step-five cooling crystallization tank
Controlling the operation in a cooling crystallizer in a heat exchange mode with a coolant partition wall, reducing the temperature of mother liquor, detecting the temperature in a tank, discharging when the temperature is reduced to 70 ℃ which is set by a system, discharging mixed crystal slurry into a centrifugal machine, and carrying out solid-liquid separation; the coolant refers to circulating water;
sixthly, a centrifuge
Separating the crystal from the mother liquor by a centrifugal machine; collecting the formed ferrous sulfate crystals, feeding the mother liquor discharged by a centrifugal machine into a feed liquor collecting tank, and regulating CuSO4After the concentration, the mixture enters a production line for continuous use;
feed liquid collecting tank
A feed liquid collecting tank, wherein the interior of the tank is divided into two independent areas, namely a copper plating solution preparation area and a copper plating solution using area; a salinity meter is arranged in the copper plating solution preparation area, the copper plating solution treated by a centrifuge firstly enters the preparation area, and CuSO with the concentration of 200g/L is added into the copper plating solution according to the density value of the copper plating solution4Solution until the density value of the copper plating solution reaches the specified value of 1.15g/cm3And lifting the prepared copper plating solution to a copper plating solution using area through an overflow pump, and finally supplementing the prepared copper plating solution into the copper plating tank according to the liquid level of the copper plating tank.
2. The application of the online recycling method of the copper plating waste liquid in the surface treatment of the metal product in the aspect of reducing the using amount of the chemical copper plating waste liquid in the claim 1; the reduction of the dosage of the chemical copper plating waste liquid refers to the fact that the Fe in the copper plating liquid is evaporated and crystallized through MVR2+After the concentration is reduced to 70g/L, the chemical copper plating solution is recycled.
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| CN115558930A (en) * | 2022-10-21 | 2023-01-03 | 深圳市捷晶科技股份有限公司 | Etching waste liquid recovery system, control method and storage medium |
| CN115593886A (en) * | 2022-12-14 | 2023-01-13 | 天津市生态环境科学研究院（天津市环境规划院、天津市低碳发展研究中心）（Cn） | Powder metallurgy sintering furnace with self-cleaning function |
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