CN103408164B - Recycling method of electroplating wastewater containing copper nitrate - Google Patents
Recycling method of electroplating wastewater containing copper nitrate Download PDFInfo
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- CN103408164B CN103408164B CN201310388177.9A CN201310388177A CN103408164B CN 103408164 B CN103408164 B CN 103408164B CN 201310388177 A CN201310388177 A CN 201310388177A CN 103408164 B CN103408164 B CN 103408164B
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Abstract
The invention provides a recycling method of electroplating wastewater containing copper nitrate and relates to the field of treatment methods of electroplating wastewater, aiming at providing a treatment method of electroplating wastewater containing copper nitrate, which is low in treatment cost, simple to operate, wide in application range, diversified in recycled products and relatively high in added value of products. The method mainly comprises the following steps: adding a small amount of distilled water into a reaction kettle to serve as base solution, starting a stirring device when the reaction temperature rises to 35-90 DEG C, adding the pre-treated electroplating wastewater containing copper nitrate and calcium oxide, calcium carbonate or calcium hydroxide slurry into the reaction kettle to react, filtering, washing, drying and sieving the reaction product to obtain an alkali type copper nitrate product, and carrying out concentration evaporating and crystallizing the filtrate to prepare a calcium nitrate product. The treatment method provided by the invention has the advantages that process flow is short, operation conditions are easily controlled, the method has safe and environment-friendly function, applicable treatment concentration range of electroplating wastewater containing copper nitrate is wide, and the method is particularly suitable for recycling copper in copper nitrate wastewater for small and medium enterprises.
Description
Technical field
The present invention relates to the treatment process field of electroplating wastewater, particularly containing its recovery method as resource of cupric nitrate electroplating wastewater.
Background technology
Plating (Electroplating) is exactly the process utilizing electrolysis principle to plate other metal or alloy of skim on some metallic surface, the technique utilizing electrolytic action to make the surface attachment layer of metal film of metal or other material, play and prevent corrosion, improve the effects such as wear resistance, electroconductibility, reflective and having improved aesthetic appearance.
Copper nitrate waste water is extensively present in field of electroplating, such as: in the much technique using copper piece as plating piece matrix, and usually all will with the cupric oxide on nitric acid removing copper piece top layer before plating; Other metal objects is when copper facing, and hanger also can plate one deck copper thereupon, accumulates over a long period, and hanger just has the thick copper of thick layer, generally needs, with salpeter solution cleaning, can produce a large amount of electroplating wastewaters containing cupric nitrate thus.The Cu of these electroplating wastewaters containing cupric nitrate often containing higher concentration
2+, H
+, NO
3 -, and the foreign matter contents such as general heavy metal are very low, if directly discharged, not only can cause the waste of resource, and can cause severe contamination to environment.
At present, to being generally adopt ion exchange method, displacement-electrolytic process or electrodeposition method to reclaim to prepare metallic copper product containing its recovery method as resource of cupric nitrate electroplating wastewater, these treatment processs all also exist the product that processing cost is higher, recovery prepares and are only metallic copper, product is too single, and the shortcoming such as added value is not relatively high.In addition, also have the following disadvantages:
Ion exchange method is due to the restriction of exchange capacity, and nitric acid has strong oxidizing property, easily destroys resin, therefore only for the recovery for lower concentration cupric nitrate.
Adopt the copper in displacement-electrolytic process recovery copper nitrate waste water, iron powder generally need be used to replace, and its method is spilled in copper nitrate waste water by iron powder, cemented out by cupric ion, cleaning post-drying, after smelting and pouring becomes plate, and refining.Adopt in this way, removal process is also more loaded down with trivial details, long flow path.
The copper mass utilizing electrodeposition method to reclaim is better, the rate of recovery is also higher, therefore lays particular stress on employing electrodeposition method containing the treatment process of cupric nitrate electroplating wastewater at present more.But the method also exists following problem: one: cupric nitrate is in the process of electrodeposition, and nitrate radical can react at anode, produce oxynitride, can operational condition be worsened, contaminate environment; Its two: higher containing concentration of nitric acid in cupric nitrate electroplating wastewater, the cathode copper of output can be anti-molten, and anode also needs special rotproofing, and technology difficulty is large, and current efficiency is low.
Summary of the invention
For the treatment process above shortcomings at present containing cupric nitrate electroplating wastewater, the object of the present invention is to provide a kind of processing cost low, simple to operate, applied widely, reclaim product diversification and the relatively high treatment process of added value of product.
For achieving the above object, the invention provides a kind of its recovery method as resource containing cupric nitrate electroplating wastewater, described is 50 ~ 130g/L containing the copper content in cupric nitrate electroplating wastewater, it is characterized in that, comprises the following steps:
(1) pre-treatment: by its pH value being adjusted to 0.5 ~ 2 to described containing adding neutralizing agent in cupric nitrate electroplating wastewater, remove insolubles, obtain clear liquid, described neutralizing agent is calcium oxide, calcium carbonate or calcium hydroxide;
(2) stirring that calcium oxide, calcium carbonate or calcium hydroxide added water is sized mixing, and after removing the larger impurity of bottom particles, furnishing massfraction counts the slurries of 3% ~ 60% with calcium oxide;
(3) in reactor, clear liquid or distilled water that a small amount of step (1) obtains is added as end liquid, when question response temperature rises to 35 ~ 90 DEG C, open whipping appts, and the slurries that clear liquid step (1) obtained and step (2) obtain are to being added to reaction kettle for reaction, feed liquid is 3 ~ 6 to adding control ph in process;
(4) feed liquid is to after adding, control temperature of reaction and pH value constant, continue reaction 10 ~ 60min, obtain reaction product;
(5) reaction product that obtains of step (4) after filtration, wash, dry, sieve after obtained basic copper nitrate product;
(6) obtained nitrocalcite product after the concentrating filter liquor evaporative crystallization that step (5) obtains.
The too low then mother liquor of copper concentration in electroplating wastewater is too many, and energy consumption of reaction increases, and production efficiency is low; Excessive concentration then viscosity is too large, and reaction has some setbacks, and copper direct yield can decline, and quality product also can by certain impact.Feed liquid controls to be because the too low generation being unfavorable for basic copper nitrate of pH value, the too high main content that can affect again copper and nitrogen in product of pH value, affects quality product 3 ~ 6 to adding pH value in process.
Further, described calcium oxide, calcium carbonate and calcium hydroxide select 200 ~ 1000 object technical grade product.
Further, the massfraction of described slurries counts 10% ~ 40% with calcium oxide.The too low then mother liquor of concentration is too many, and energy consumption increases, and concentration is too high, and react too fast, pH is wayward, and particle can be very tiny, affects strainability and the mobility of product.
Further, press filtration or centrifugal is filtered into described in.
Further, the bake out temperature of described reaction product is 70 ~ 120 DEG C.
Beneficial effect:
compared with prior art, treatment process technical process provided by the invention is short, processing unit is simple, operational condition is easy to control, processing cost is low, safety and environmental protection, the concentration range containing cupric nitrate electroplating wastewater that is suitable for processing are comparatively wide, is especially applicable to the recovery that medium and small sized enterprises realize copper in copper nitrate waste water.
Separately, treatment process provided by the invention can prepare basic copper nitrate and reclaim nitrocalcite, basic copper nitrate can be widely used in pyrotechnics, propelling agent, brass work intermediate and the various fields such as the oxygenant preparing air bag propellant, its market requirement breach is always very large, from this meaning, basic copper nitrate added value of product is relatively high.
To sum up, the present invention not only solves a difficult problem for the copper nitrate waste water process of electroplating industry, and provide a new thinking for the compound probability of basic copper nitrate, to contain cupric nitrate electroplating wastewater for raw material, with cheap, the calcium oxide that concentration variable range is wide, basic copper nitrate is prepared in calcium carbonate or calcium hydroxide slurry reaction, its reaction process comparatively relaxes, output product strainability is good, good product mobility after dry, gained basic copper nitrate product purity is high, quality is up to state standards, and reaction process does not need to add any ammonium salt or complexing agent, wastewater treatment is comparatively simple.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the product adopting method provided by the invention to obtain.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and following examples are explanation of the invention, and the present invention is not limited to following examples.
Embodiment 1
reactions steps is as follows: be mixed with 1000 order technical grade calcium carbonate massfraction to count 60% suspension liquid with calcium oxide, and in advance will (cupric is about 50g/L containing cupric nitrate electroplating wastewater with this suspension liquid, pH=0.3) pH value is transferred to 1.5, removes insolubles, obtains clear liquid; Then in reactor, a small amount of distilled water is added, and open whipping appts, temperature is increased to 35 DEG C simultaneously, and then will the clear liquid of pH and calcium carbonate suspension liquid (enough) be mixed up simultaneously to being added in reactor, control ph is 6.0, and the rear maintenance pH that fed in raw material continues to stir 20min, and product filters, washing, dry at 100 DEG C, pulverize 60 mesh sieves, finally obtain finished product; Obtained nitrocalcite product after concentrating filter liquor evaporative crystallization after product filters.
Detected crystal composition and the structure of finished product by XRD detection method, can determine that finished product is basic copper nitrate; The finished product of chemical analysis detection simultaneously obtains: copper content 52.92%, nitrate is (with NO
3meter) content 25.84%, sodium content 0.05%, the deposition rate 98.45% of copper, the XRD figure spectrum of product is consistent with standard diagram.
Embodiment 2
reactions steps is as follows: be mixed with 700 order technical grade calcium carbonate massfraction to count 20% suspension liquid with calcium oxide, and in advance will (cupric is about 80g/L containing cupric nitrate electroplating wastewater with this suspension liquid, pH=0.3) pH value is transferred to 1.0, removes insolubles, obtains clear liquid; Then in reactor, a small amount of distilled water is added, and open whipping appts, temperature is increased to 50 DEG C simultaneously, and then will the clear liquid (400ml) of pH and calcium carbonate suspension liquid (enough) be mixed up simultaneously to being added in reactor, control pH is 4.5, and the rear maintenance pH that fed in raw material continues to stir 40min, and product filters, washing, dry at 105 DEG C, pulverize 60 mesh sieves, finally obtain finished product; Obtained nitrocalcite product after concentrating filter liquor evaporative crystallization after product filters.
Detected crystal composition and the structure of finished product by XRD detection method, can determine that finished product is basic copper nitrate; The finished product of chemical analysis detection simultaneously obtains: copper content 52.78%, nitrate is (with NO
3meter) content 25.36%, calcium contents 0.1%, the deposition rate 98.65% of copper, the XRD figure spectrum of product is consistent with standard diagram.
Embodiment 3
reactions steps is as follows: be mixed with SILVER REAGENT unslaked lime massfraction to count 40% suspension liquid with calcium oxide, and in advance the pH value containing cupric nitrate electroplating wastewater (cupric is about 130g/L, pH=0.3) be transferred to 2.0, remove insolubles, obtain clear liquid; Then in reactor, a small amount of distilled water is added, and open whipping appts, temperature is increased to 70 DEG C simultaneously, and then will the clear liquid of pH and calcium hydroxide suspension liquid (enough) be mixed up simultaneously to being added in reactor, control pH is 4.0, and the rear maintenance pH that fed in raw material continues to stir 30min, and product filters, washing, dry at 70 DEG C, pulverize 60 mesh sieves, finally obtain finished product; Obtained nitrocalcite product after concentrating filter liquor evaporative crystallization after product filters.
Detected crystal composition and the structure of finished product by XRD detection method, can determine that finished product is basic copper nitrate; The finished product of chemical analysis detection simultaneously obtains: copper content 52.92%, nitrate is (with NO
3meter) content 25.44%, calcium contents 0.06%, the deposition rate 99.13% of copper, the XRD figure spectrum of product is consistent with standard diagram.
Embodiment 4
reactions steps is as follows: be mixed with 200 order technical grade unslaked limes massfraction to count 3% suspension liquid with calcium oxide,, and in advance the pH value containing cupric nitrate electroplating wastewater (cupric is about 130g/L, pH=0.3) is transferred to 0.5, remove insolubles, obtain clear liquid; Then in reactor, a small amount of distilled water is added, and open whipping appts, temperature is increased to 90 DEG C simultaneously, and then will the clear liquid of pH and calcium hydroxide suspension liquid (enough) be mixed up simultaneously to being added in reactor, control pH is 3, and the rear maintenance pH that fed in raw material continues to stir 60min, and product filters, washing, dry at 90 DEG C, pulverize 60 mesh sieves, finally obtain finished product; Obtained nitrocalcite product after concentrating filter liquor evaporative crystallization after product filters.
Detected crystal composition and the structure of finished product by XRD detection method, can determine that finished product is basic copper nitrate.The finished product of chemical analysis detection simultaneously obtains: copper content 52.82%, nitrate is (with NO
3meter) content 25.83%, sodium content 0.05%, the deposition rate 98.43% of copper, the XRD figure spectrum of product is consistent with standard diagram.
Embodiment 5
reactions steps is as follows: be mixed with 400 order technical grade white limes massfraction to count 10% suspension liquid with calcium oxide, and in advance will (cupric is about 130g/L containing cupric nitrate electroplating wastewater, pH=0.3) pH value is transferred to 1.5, removes insolubles, obtains clear liquid; Then in reactor, a small amount of distilled water is added, and open whipping appts, temperature is increased to 90 DEG C simultaneously, and then will the clear liquid of pH and calcium hydroxide suspension liquid (enough) be mixed up simultaneously to being added in reactor, control pH is 3.5, and the rear maintenance pH that fed in raw material continues to stir 10min, and product filters, washing, dry at 100 DEG C, pulverize 60 mesh sieves, finally obtain finished product; Obtained nitrocalcite product after concentrating filter liquor evaporative crystallization after product filters.
Detected crystal composition and the structure of finished product by XRD detection method, can determine that finished product is basic copper nitrate; The finished product of chemical analysis detection simultaneously obtains: copper content 52.51%, nitrate is (with NO
3meter) content 25.16%, sodium content 0.03%, the deposition rate 99.42% of copper, the XRD figure spectrum of product is consistent with standard diagram.
Claims (5)
1., containing its recovery method as resource of cupric nitrate electroplating wastewater, described is 50 ~ 130g/L containing the copper content in cupric nitrate electroplating wastewater, it is characterized in that, comprises the following steps:
(1) pre-treatment: by its pH value being adjusted to 0.5 ~ 2 to described containing adding neutralizing agent in cupric nitrate electroplating wastewater, remove insolubles, obtain clear liquid, described neutralizing agent is calcium oxide, calcium carbonate or calcium hydroxide;
(2) stirring that calcium oxide, calcium carbonate or calcium hydroxide added water is sized mixing, and after removing the larger impurity of bottom particles, furnishing massfraction counts the slurries of 3% ~ 60% with calcium oxide;
(3) in reactor, clear liquid or distilled water that a small amount of step (1) obtains is added as end liquid, when question response temperature rises to 35 ~ 90 DEG C, open whipping appts, and the slurries that clear liquid step (1) obtained and step (2) obtain are converted and are added to reaction kettle for reaction, feed liquid converts that to add control ph in process be 3 ~ 6;
(4) after feed liquid is converted and is added, control temperature of reaction and pH value constant, continue reaction 10 ~ 60min, obtain reaction product;
(5) reaction product step (4) obtained after filtration, wash, dry, sieve after obtained basic copper nitrate product;
(6) obtained nitrocalcite product after concentrating filter liquor evaporative crystallization step (5) obtained.
2. its recovery method as resource according to claim 1, is characterized in that: described calcium oxide, calcium carbonate and calcium hydroxide select 200 ~ 1000 object technical grade product.
3. its recovery method as resource according to claim 1, is characterized in that: the massfraction of described slurries counts 10% ~ 40% with calcium oxide.
4. its recovery method as resource according to claim 1, is characterized in that: described in be filtered into press filtration or centrifugal.
5. its recovery method as resource according to claim 1, is characterized in that: the bake out temperature of described reaction product is 70 ~ 120 DEG C.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104894564B (en) * | 2015-05-05 | 2018-02-27 | 秦禹科技股份有限公司 | Decoating liquid regeneration method in a kind of electroplating wastewater |
| CN107266129B (en) * | 2017-07-18 | 2020-12-01 | 深圳市深投环保科技有限公司 | Method for recovering copper nitrate-containing wastewater and method for preparing urea ammonium nitrate liquid fertilizer |
| CN107699697A (en) * | 2017-10-19 | 2018-02-16 | 惠州市臻鼎环保科技有限公司 | A kind of copper recovery method of copper nitrate waste water |
| CN108033480A (en) * | 2017-12-12 | 2018-05-15 | 合肥学院 | Method for recycling copper in wastewater by using calcium carbonate |
| CN111187099A (en) * | 2019-07-11 | 2020-05-22 | 深圳市深投环保科技有限公司 | Preparation method of calcium nitrate-containing secondary element water-soluble fertilizer liquid product |
| CN115072763A (en) * | 2021-04-29 | 2022-09-20 | 阮氏化工（常熟）有限公司 | Device and method for producing basic copper nitrate by using copper-containing stripping and hanging liquid |
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| US4105743A (en) * | 1976-06-15 | 1978-08-08 | Mx-Processer Reinhardt & Co. Ab | Selectively extracting copper, zinc, nickel from a mixture of metal hydroxides |
| CN101372746A (en) * | 2007-08-23 | 2009-02-25 | 三合资源科技控股有限公司 | Copper resource cyclic regeneration method in manufacture process |
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| US4105743A (en) * | 1976-06-15 | 1978-08-08 | Mx-Processer Reinhardt & Co. Ab | Selectively extracting copper, zinc, nickel from a mixture of metal hydroxides |
| CN101372746A (en) * | 2007-08-23 | 2009-02-25 | 三合资源科技控股有限公司 | Copper resource cyclic regeneration method in manufacture process |
| CN102557299A (en) * | 2012-01-11 | 2012-07-11 | 浙江海拓环境技术有限公司 | Recovery method of copper-nickel heavy metals in electroplated mixed-flow waste water |
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