CN102206849B - Device for removing harmful impurities from chromeplating solution - Google Patents
Device for removing harmful impurities from chromeplating solution Download PDFInfo
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- CN102206849B CN102206849B CN201110106397.9A CN201110106397A CN102206849B CN 102206849 B CN102206849 B CN 102206849B CN 201110106397 A CN201110106397 A CN 201110106397A CN 102206849 B CN102206849 B CN 102206849B
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Abstract
The invention discloses a device for removing harmful impurities from chromeplating solution. The device comprises an anode chamber and a cathode chamber, wherein the anode chamber is used for storing the chromeplating solution to be treated and the cathode chamber is used for storing electrolyte. A method for preparing the cathode chamber comprises the following steps of: uniformly stirring diatomite, sulfoacid-type homogeneous-phase cation selective material and adhesive in a weight ratio of 5: 4: 1; extruding and forming; stoving at the temperature of 90 DEG C; and drying to obtain the cathode chamber. The device can purify aged and wasted chromeplating solution and the purified chromeplating solution can be reused, so that the pollution of emission to the environment is avoided and the pressure of the environment treatment work of the aged and wasted chromeplating solution is reduced; and the device purifies the chromeplating solution at high speed and is convenient to run and low in cost.
Description
Technical field
The present invention relates to a kind of device removing harmful impurities from chromeplating solution, relate to electroplating technology field.
Background technology
Cr-plating Bath comprises decorative chromium plating solution and function chromium plating solution (hard chrome plating solution).Impurity harmful in Cr-plating Bath has: iron ion, cupric ion, excessive trivalent chromic ion, calcium ion, nickel ion, zine ion, sodium ion, potassium ion, chlorion, nitrate ion etc.Harmful ion total content is more than after 15 grams per liters, and plating solution cannot normally be electroplated, and bright range narrows, and depth capability declines, and covering power is deteriorated, and current efficiency reduces.The too high rear plating solution of foreign matter content is scrapped, and brings severe stress to environmental treatment work.
At present, hexavalent chromium plating, sexavalent chrome is heavy metal, can draw middle perforation of nasal septum, stomach illness, white cell decline, asthma pulmonary lesion, " chrome ulcer " etc. and have carcinogenesis to some position of human body, very big to environmental hazard.In recent years, although have the successful process of surface treatment that much can replace sexavalent chrome chromium plating, the certainty that hexavalent chromium plating has it to exist, be still a kind of peculiar plating that can not lack in some field.Since there is it to there is certainty, can not ban completely again, so be necessary that the pollution to this plating of hexavalent chromium plating brings environment prevents, prevents and processes.
At present, the way of purification Cr-plating Bath uses biscuit ware cylinder, and this way only adopts electromigration to collect, and speed is quite slow.Another kind of way uses Zeo-karb, and resin is easily aging, complicated operation, and running cost is very high.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of device removing harmful impurities from chromeplating solution, adopts following technical scheme:
A kind of device removing harmful impurities from chromeplating solution, comprise anolyte compartment and cathode compartment, anolyte compartment is for holding pending Cr-plating Bath, cathode compartment holds electrolytic solution, the making method of described cathode compartment is: according to weight ratio diatomite: sulfonic acid type homogeneous phase cation selective material: sizing agent=5: 4: 1 ratios stir, through extruding postforming, then obtain through 90 DEG C of oven dry, drying.
Described device, described electrolytic solution is 5-50 grams per liter sulfuric acid and 20-100 grams per liter chromic anhydride.
This device can make the aging Cr-plating Bath scrapped be purified, and the Cr-plating Bath after purification can come into operation again, avoids discharging pollution on the environment, alleviates the pressure to aging Cr-plating Bath environmental treatment work of scrapping.Solution is wiped in this device purification chromium plating, and not only speed is fast, and runs conveniently, and cost is low again.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram of the embodiment of the present invention 1;
Fig. 2 is the apparatus structure schematic diagram of the embodiment of the present invention 2;
Fig. 3 is the apparatus structure schematic diagram of the embodiment of the present invention 3.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
With reference to figure 1, the device of removal harmful impurities from chromeplating solution of the present invention comprises anolyte compartment 6 and cathode compartment 5 (also claiming ion cylinder).Anolyte compartment 6 is for holding pending Cr-plating Bath 2, cathode compartment holds electrolytic solution 4, electrolytic solution is 5-50 grams per liter sulfuric acid and 20-100 grams per liter chromic anhydride, detrimental impurity is collected in cathode compartment 5, negative electrode 1 adopts the materials such as lead, lead antimony alloy, terne metal, iron plate, stainless steel plate or titanium or titanium alloy, and anode 3 adopts lead, terne metal, lead antimony alloy or titanium or titanium alloy material.
Cathode compartment 5 uses diatomite and sulfonic acid type homogeneous phase cation selective material (the perfluorosulfonic acid type homogeneous phase cation selective material (film) of Dupont or Japanese rising sun sound field), and by chemically stable sizing agent (such as PMUF Resin adhesive, Epoxy adhesive, Tracon company of the U.S. releases Tra-BondF202 bi-component epoxide-resin sizing agent, K mono-600-31 self-vulcanizing gluing agent etc.), according to weight ratio diatomite: sulfonic acid type homogeneous phase cation selective material: sizing agent=5: 4: 1 ratios stir, through extruding postforming, again through 90 DEG C of oven dry, dry obtained.
Diatomite main component is silicon-dioxide, high-quality is white, content is more than 70%, the water white diatomite of prioritizing selection monomer, this kind of diatomite have exquisiteness, light weight, loose (density is 0.3-0.5 gram/cc), porous, hole are large, absorptivity is strong and perviousness is strong, be conducive to the fixing of homogeneous phase ion selectivity material, be more conducive to passing through and collecting of ion; This diatomite also has corrosion-resistant, resistance to oxidation, heatproof, the feature such as wear-resisting, is applicable to being soaked in having in the Cr-plating Bath of strong oxidizing property.Play the effect of infiltration and collection foreign ion.
Homogeneous phase cation selective material in cathode compartment, the macromolecular material with selective penetrated property is made, and this kind of homogeneous phase cation selective membrane is sulfonic acid type, sulfonic acid type be highly acid, exist stable at Cr-plating Bath.
After powered up, under electric field action, the positively charged ion with positive charge just can by the homogeneous phase cation selective material in cathode compartment, and negatively charged ion because the same sex repels not by, so have selective penetrated property.Like this under electric field action, the positively charged ion in Cr-plating Bath: iron ion, cupric ion, trivalent chromic ion, hexavalent chromium, calcium ion, nickel ion, zine ion, sodium ion, potassium ion, chlorion, nitrate ion etc. can be collected in the cathodic compartment and be removed.
Anolyte compartment utilizes the electrochemical reaction of anode own, and trivalent chromium oxidation is become sexavalent chrome; Chlorion is oxidized to chlorine, and nitrate ion is oxidized to ammonia, and anode 3 preferably adopts terne metal material.
Embodiment 2
1000 liters of Cr-plating Baths, containing chromic anhydride 289.654 grams per liter, sulfuric acid 3.2 grams per liter, iron ion 6.682 grams per liter, cupric ion 8.678 grams per liter, trivalent chromium 9.6 grams per liter.Now plating solution depth capability is poor, and luminance brightness is poor, and covering power is poor, and plating speed is slow, and cathode efficiency is not 8% (using additive).
Adopt two cell processing groups to process, see Fig. 2.The electrolytic solution configured in cathode compartment ion cylinder is 50 grams per liter sulfuric acid and 50 grams per liter chromic anhydrides, electric current 150A/dm
2, voltage 10V.Process after 12 hours, electric current is increased to 200A/dm
2, voltage is down to 8V; Assay concentration: containing chromic anhydride 289.112 grams per liter, sulfuric acid 3.2 grams per liter, iron ion 3.344 grams per liter, cupric ion 4.351 grams per liter, trivalent chromium 6.8 grams per liter.
Replacing reconfigures ion cylinder electrolyte inside, and continue electrolysis 12 hours, electric current rises to 260A/dm2, voltage is down to 5.6V, assay concentration: containing chromic anhydride 289.110 grams per liter, sulfuric acid 3.2 grams per liter, iron ion 1.865 grams per liter, cupric ion 0.891 grams per liter, trivalent chromium 2.568 grams per liter.
Replacing reconfigures ion cylinder electrolyte inside, and continue electrolysis after 7 days, electric current rises to 290A/dm2, and voltage is down to 4.5V, assay concentration: containing chromic anhydride 289.110 grams per liter, sulfuric acid 3.2 grams per liter, iron ion 0.002 grams per liter, trivalent chromium 0.0062 grams per liter.
Now plating solution hangs workpiece electrolysis 4-6 hour, rear normal work, current efficiency 12%, and coating light, depth capability is good, and covering power is good.
Experiment shows, change the electrolytic solution cycle shorter, frequency number of times is more, and impurity treatment speed is faster.
Embodiment 3
1000 liters of Cr-plating Baths, containing chromic anhydride 250.6856 grams per liters, sulfuric acid 2.7 grams per liter, iron ion 9.321 grams per liter, cupric ion 15.3511 grams per liter, trivalent chromium 11.6895 grams per liter.Now plating solution depth capability does not have, luminance brightness burnt hair, covering power extreme difference, and plating speed is slow, and cathode efficiency is 18% (using HEEC additive).
Adopt four cell processing group process, see Fig. 3.Configuring electrolytic solution in ion cylinder is 5 grams per liter sulfuric acid and 100 grams per liter chromic anhydrides, electric current 280A/dm2, voltage 12V.Process after 12 hours, electric current rises to 350A/dm2, and voltage is down to 11V assay: containing chromic anhydride 250.6856 grams per liter, sulfuric acid 2.7 grams per liter, iron ion 7.6520 grams per liter, cupric ion 10.6352 grams per liter, trivalent chromium 9.4231 grams per liter.
Adopt identical electrolytic solution, change ion cylinder electrolyte inside, continue electrolysis 12 hours, electric current rises to 380A/dm2, and voltage is down to 10V assay: containing chromic anhydride 250.6800 grams per liter, sulfuric acid 2.7 grams per liter, iron ion 5.4851 grams per liter, cupric ion 7.6354 grams per liter, trivalent chromium 6.5311 grams per liter.
Replacing reconfigures ion cylinder electrolyte inside, and continue electrolysis after 7 days, electric current rises to 350A/dm2, voltage is down to 11V assay: containing chromic anhydride 250.6762 grams per liter, sulfuric acid 2.7 grams per liter, iron ion 0.6520 grams per liter, cupric ion 1.6352 grams per liter, trivalent chromium 2.6524 grams per liter.
Experiment shows, processing unit group is more, and processing speed is faster, and general 1000 liters of tank liquors are after 7-10 days electrolysis treatment, almost the same with the plating solution of new preparation.
Now plating solution hangs workpiece plating work, and current efficiency 27.5%, coating luminance brightness green light, depth capability is good, and covering power is good.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (2)
1. remove the device of harmful impurities from chromeplating solution for one kind, it is characterized in that, comprise anolyte compartment and cathode compartment, anolyte compartment is for holding pending Cr-plating Bath, cathode compartment holds electrolytic solution, the making method of described cathode compartment is: according to weight ratio diatomite: sulfonic acid type homogeneous phase cation selective material: sizing agent=5: 4: 1 ratios stir, and through extruding postforming, then obtains through 90 DEG C of oven dry, drying.
2. device according to claim 1, is characterized in that, described electrolytic solution is 5-50 grams per liter sulfuric acid and 20-100 grams per liter chromic anhydride.
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| CN201110106397.9A CN102206849B (en) | 2011-04-27 | 2011-04-27 | Device for removing harmful impurities from chromeplating solution |
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| CN201110106397.9A CN102206849B (en) | 2011-04-27 | 2011-04-27 | Device for removing harmful impurities from chromeplating solution |
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| CN102560614A (en) * | 2012-02-06 | 2012-07-11 | 太原特益达科技有限公司 | Equipment for removing harmful impurities from chromium plating solution |
| CN105568355A (en) * | 2014-11-05 | 2016-05-11 | 天津市津一电镀有限公司 | Method and device for purifying chromium plating solution and waste liquor thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642863A (en) * | 2002-01-22 | 2005-07-20 | 埃克塞基技术公司 | Advanced electrodeionization for fluid recycling |
| CN101177789A (en) * | 2007-07-25 | 2008-05-14 | 徐建中 | Device for processing foreign ion in chromium plating liquid |
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| NZ331053A (en) * | 1998-07-21 | 2002-12-20 | Osmose New Zealand | Process for electrochemical generation of higher oxidate state values from lower oxidation state values above zero of transition metal(s) [eg; |
| DE102004038693B4 (en) * | 2004-08-10 | 2010-02-25 | Blasberg Werra Chemie Gmbh | Apparatus and method for removing foreign matter from process solutions and process for regenerating a cation exchanger |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642863A (en) * | 2002-01-22 | 2005-07-20 | 埃克塞基技术公司 | Advanced electrodeionization for fluid recycling |
| CN101177789A (en) * | 2007-07-25 | 2008-05-14 | 徐建中 | Device for processing foreign ion in chromium plating liquid |
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