CN108341424B - Method for producing copper sulfate - Google Patents
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- CN108341424B CN108341424B CN201810273907.3A CN201810273907A CN108341424B CN 108341424 B CN108341424 B CN 108341424B CN 201810273907 A CN201810273907 A CN 201810273907A CN 108341424 B CN108341424 B CN 108341424B
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Abstract
The invention discloses a production method of copper sulfate, which comprises the following steps: adding an oxidant into the acidic etching waste liquid to oxidize cuprous ions and ferrous ions in the acidic etching waste liquid, then adjusting the pH value to 1.7-1.9, stirring for reaction, adding activated carbon, settling and layering, taking supernatant, and filtering to obtain the impurity-removed acidic etching waste liquid; adding soluble magnesium salt into the alkaline etching waste liquid, stirring for reaction, settling and layering, and filtering the supernatant to obtain the alkaline etching waste liquid after impurity removal; mixing and reacting the acid etching waste liquid and the alkaline etching waste liquid after impurity removal to obtain basic copper chloride; converting the basic copper chloride ammonia into copper hydroxide, then filtering, washing water for purification, and pulping; and adding sulfuric acid to acidify until the pH value is 0.5-1.0, and then carrying out hot filtration, cooling crystallization, solid-liquid separation and drying treatment to obtain copper sulfate. The copper sulfate produced by the method can reach the standard of electroplating grade, and the recovery rate of copper in the etching waste liquid is high.
Description
Technical Field
The invention relates to a production method of copper sulfate, belonging to the technical field of copper sulfate production processes.
Background
The etching waste liquid is generated in the process of dissolving copper by a chemical corrosion method in the etching process of a Printed Circuit Board (PCB), and can be further divided into acid etching waste liquid and alkaline etching waste liquid according to the acidity and alkalinity, wherein the content of copper in the acid etching waste liquid is about 30 g/L-160 g/L, and the content of copper in the alkaline etching waste liquid is about 40 g/L-170 g/L.
With the rapid development of the electronic industry, tens of thousands of tons of etching waste liquid are generated in China every year, and if the etching waste liquid is not properly treated and utilized, serious environmental pollution and great economic waste can be caused. The domestic common treatment method comprises the following steps: extracting copper from the acid and alkali etching waste liquid to produce basic copper chloride, copper sulfate, copper oxide and other products.
At present, electroplating-grade copper sulfate used as an electroplating additive is almost produced by taking circuit board copper-containing etching waste liquid as a raw material, but the quality of a copper sulfate crude product prepared by the traditional copper sulfate production process does not reach the standard, contains more impurities and metal ions, and does not meet the electroplating-grade standard of copper sulfate.
Disclosure of Invention
Based on this, there is a need for a method for producing copper sulfate that meets plating-grade standards.
A method for producing copper sulfate comprises the following steps:
adding an oxidant into the acidic etching waste liquid to oxidize cuprous ions and ferrous ions in the acidic etching waste liquid, then adjusting the pH value to 1.7-1.9, stirring for reaction, adding activated carbon, settling and layering, and then taking supernatant for filtering treatment to obtain the impurity-removed acidic etching waste liquid;
adding soluble magnesium salt into the alkaline etching waste liquid, stirring for reaction, settling and layering, and filtering the supernatant to obtain the alkaline etching waste liquid after impurity removal;
mixing and reacting the impurity-removed acidic etching waste liquid and the impurity-removed alkaline etching waste liquid to obtain basic copper chloride;
reacting the basic copper chloride with ammonia water to generate a precipitate, filtering to obtain filter residue, purifying by washing water, adding water, and pulping to obtain copper hydroxide slurry;
adding sulfuric acid into the copper hydroxide slurry, adjusting the pH value of the copper hydroxide slurry to 0.5-1.0, and performing heat filtration treatment to obtain a mixed solution containing copper sulfate; and (3) cooling and crystallizing the mixed solution containing copper sulfate, performing solid-liquid separation to obtain copper sulfate crystals, and drying.
In one embodiment, the reagent for adjusting the pH value to 1.7-1.9 is ammonia water. Adjusting the pH value to 1.7-1.9 with ammonia water to generate copper sludge (Cu (OH)2·CuCl2) The precipitate such as ferric arsenate is easy to be adsorbed for co-precipitation, and other impurities can be avoided from being brought in.
In one embodiment, the mass volume ratio of the using amount of the activated carbon to the acidic etching waste liquid is (0.2-0.3) g: 1L. The using amount of the activated carbon is mainly determined according to the volume of the acidic etching waste liquid and the amount of organic impurities in the acidic etching waste liquid, and the organic impurities in the acidic etching waste liquid can be effectively removed by adding 0.2-0.3 g of activated carbon into 1L of the acidic etching waste liquid.
In one embodiment, the baume degree of the acid etching waste liquid after impurity removal is 24 Be-30 Be DEG, and the pH value is 1.0-1.5.
In one embodiment, the Baume degree of the alkaline etching waste liquid after impurity removal is 12 Be-20 Be degrees, and the pH value is 8.0-9.0.
In one embodiment, in the step of reacting the copper oxychloride and ammonia water to generate a precipitate, the concentration of the ammonia water is 20 wt%, and the volume-to-weight ratio of the amount of the ammonia water to the copper oxychloride is (1.2-1.3) L:1 Kg. Ammonia water with the mass concentration of 20% reacts with the basic copper chloride to carry out ammonia conversion, and 1.2L-1.3L of ammonia water reacts with every 1Kg of basic copper chloride to completely convert into copper hydroxide.
In one embodiment, the concentration of sulfuric acid is greater than or equal to 98 wt%. A large amount of heat is generated in the process of carrying out acidification reaction on copper hydroxide slurry by using concentrated sulfuric acid, the temperature of a reaction system is higher and higher along with the acidification, the solubility of copper sulfate in the reaction system is higher and higher, and thus, when the acidification is complete, namely the pH value of the reaction system is 0.5-1.0, the temperature of the reaction system reaches about 100 ℃, and heat can be provided for the subsequent crystallization reaction of the copper sulfate.
In one embodiment, the step of mixing and reacting the impurity-removed acidic etching waste liquid and the impurity-removed alkaline etching waste liquid to obtain the basic copper chloride specifically comprises the following steps:
firstly, respectively preheating the acid etching waste liquid after impurity removal and the alkaline etching waste liquid after impurity removal to 43-55 ℃, then mixing the acid etching waste liquid and the alkaline etching waste liquid in the presence of basic copper chloride seed crystals, and reacting the acid etching waste liquid and the alkaline etching waste liquid at the temperature of 68-72 ℃ and the stirring speed of 65-85 r/min to obtain the basic copper chloride. Therefore, the reaction conditions are strictly controlled, the basic copper chloride is crystallized faster, the production efficiency is improved, and meanwhile, the obtained basic copper chloride crystal has uniform particles, good fluidity and easy filter pressing, and the doped impurities are few.
In one embodiment, in the reaction process of the acid etching waste liquid after impurity removal and the alkaline etching waste liquid after impurity removal, the acid etching waste liquid after impurity removal and preheating and the alkaline etching waste liquid after impurity removal and preheating are continuously added, so that the pH value of the acid etching waste liquid and the alkaline etching waste liquid is 4.30-5.00 when the acid etching waste liquid and the alkaline etching waste liquid react. Therefore, by controlling the pH value of the reaction system to be 4.30-5.00, the recovery rate of copper in the etching waste liquid can be improved, and the content of impurities in the basic copper chloride is low.
In one embodiment, the flow rate of the continuously added preheated acidic waste etching solution and preheated alkaline waste etching solution is controlled to be 2-6 cubic/hour. Therefore, by controlling the flow of the acidic etching waste liquid and the alkaline etching waste liquid into the reactor to be within the range of 2-6 cubic/hour, the pH of the reaction system can be well adjusted to be 4.30-5.00, and other pH regulators are not required to be added, so that the procedure is simplified, and other ionic impurities brought by using other pH regulators are avoided. And can react copper ions and chloride ions in the acidic etching waste liquid with copper ammonia chloride complex and ammonia water in the alkaline etching waste liquid to obtain the basic copper chloride crystal with better crystal form.
The method removes metal ions such as iron, aluminum and the like, arsenic, organic impurities and other water insoluble matters in the acid etching waste liquid and the alkaline etching waste liquid respectively by removing impurities from the acid etching waste liquid and the alkaline etching waste liquid, strictly controls each reaction condition in the production process, and removes chloride ions, ammonia salts, sulfate ions and the like respectively by performing washing water purification and other treatments on intermediate products, so that the produced copper sulfate reaches the electroplating grade standard.
Further, in the step of neutralization reaction of the acidic etching waste liquid and the alkaline etching waste liquid, the acidic etching waste liquid and the alkaline etching waste liquid are respectively preheated to 43-55 ℃, so that the temperature difference between the raw materials and the crystallization reaction is reduced, the reaction instability is avoided, basic copper chloride seed crystals are added to promote the formation of crystals, and the proper reaction temperature, pH value and stirring speed are controlled, so that the basic copper chloride is high in crystallization speed, the produced basic copper chloride is high in purity, good in particle flow and easy to filter, and the recovery rate of copper in the etching waste liquid is high.
Then the high-purity basic copper chloride reacts with ammonia water to generate copper hydroxide precipitate which is beneficial to filtering, washing water purification and pulping, and the washing water purification is carried out to remove chloride ions and ammonium salts to obtain high-purity copper hydroxide slurry, so that the purity of copper sulfate generated by subsequent acidification and crystallization can meet the requirement of electroplating grade.
Drawings
FIG. 1 is a flow chart of the process for producing copper sulfate according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
As shown in fig. 1, the method for producing copper sulfate according to an embodiment of the present invention includes the steps of:
s1, adding an oxidant into the acidic etching waste liquid to oxidize cuprous ions and ferrous ions in the acidic etching waste liquid, then adjusting the pH value to 1.7-1.9, stirring for reaction, adding activated carbon, settling and layering, and then taking supernatant for filtering treatment to obtain the impurity-removed acidic etching waste liquid.
Specifically, an oxidant is added into the acidic etching waste liquid until the solution is green and transparent, and the oxidizing end point is the oxidizing end point, cuprous ions in the acidic etching waste liquid are oxidized into bivalent copper ions, ferrous ions are oxidized into trivalent ferric ions, and arsenite radicals are oxidized into arsenate radicals. The arsenate reacts with iron ions, aluminum ions and the like in the acidic etching waste liquid to generate stable ferric arsenate and aluminum arsenate precipitates. If the color of the acidic etching waste liquid is black and opaque, the oxidant needs to be added continuously until the solution is green and transparent. It will be appreciated that the determination of whether the oxidation endpoint has been reached may also be made by, for example, sampling cuprous and ferrous iron in the sample.
Further, the pH value of the acidic etching waste liquid is regulated and is strictly controlled to be 1.7-1.9, and the acidic etching waste liquid is stirred and reacts for 0.5-3 hours. A small amount of divalent copper ions in the acidic etching waste liquid are converted into copper mud, and ferric arsenate and aluminum arsenate are adsorbed to be subjected to coprecipitation. Then adding a proper amount of active carbon to adsorb organic impurities in the acidic etching waste liquid, standing for about 10 hours, settling, layering and filtering to remove water-insoluble substances such as ferric arsenate, aluminum arsenate, copper sludge, organic impurities and the like, thereby obtaining the acidic etching waste liquid meeting the production requirements of electroplating-grade copper sulfate. It can be understood that in order to meet the requirements of etching quality and performance in the PCB etching process, organic compounds are generally added into the etching solution to further improve the etching quality and rate, so that the etching solution contains organic compounds, and these organic additives are often difficult to separate, so that in order to ensure the purity of copper sulfate, an appropriate amount of activated carbon with strong adsorption capacity is added to remove organic impurities in the etching solution by adsorption.
In one embodiment, the oxidizer is selected from at least one of sodium chlorate, hydrogen peroxide, and potassium chlorate.
In one embodiment, the oxidizing agent is sodium chlorate. Furthermore, sodium chlorate solution with the concentration of 0.2 g/L-0.3 g/L is used as the oxidant. Thus, cuprous in the acidic etching waste liquid is converted into bivalent copper: 6Cu++ClO3-+6H+→6Cu2++3H2O + Cl-; conversion of ferrous iron to ferric iron: 6Fe2++ClO3-+6H+→6Fe3++3H2O + Cl-; conversion of arsenite to arsenate: AsO3 3-+ClO3-+4H+→AsO4 3-+Cl-+2H2O。
In one embodiment, the pH value is adjusted to 1.7-1.9 by ammonia water, and the mixture is stirred and reacted for about 2 hours, so that ferric arsenate precipitates in the acidic etching waste liquid and copper sludge are subjected to co-precipitation.
Reacting iron ions in the acidic etching waste liquid with arsenate to generate ferric arsenate: fe3++AsO4 3-→FeAsO4↓, aluminum ions in the acidic etching waste liquid react with arsenate radicals to generate aluminum arsenate: al (Al)3++AsO4 3-→AlAsO4↓. The pH of the acidic etching waste liquid is adjusted to 1.7 by using ammonia water1.9, reacting a small amount of chloride ions and copper ions in the acidic etching waste liquid with ammonia water to generate copper sludge: 2CuCl2+2NH3·H2O→Cu(OH)2·CuCl2↓+2NH4Cl and copper sludge adsorb ferric arsenate and aluminum arsenate, and are subjected to coprecipitation together to remove impurities such as arsenic, iron, aluminum and the like. Meanwhile, the pH is adjusted by ammonia water, no new impurity is introduced, basic copper chloride mother liquor generated in the subsequent basic copper chloride generation step is convenient to recycle, and the sewage treatment pressure can be further reduced.
In the test process, the inventor finds that when the pH value of the acidic etching waste liquid is adjusted to be 2.5 or more by adding ammonia water, the generation amount of coprecipitation is obviously increased, which indicates that a large amount of copper ions react with the ammonia water to generate copper mud, and the recovery rate of copper in the etching waste liquid is greatly reduced.
In one embodiment, the weight volume ratio of the amount of the activated carbon to the acidic waste etching solution to be treated is (0.2-0.3) g: 1L. It can be understood that 0.2g to 0.3g of activated carbon is added into every 1 liter of acidic etching waste liquid, so that organic impurities in the etching waste liquid can be effectively adsorbed, and the effect of removing the organic impurities is achieved.
In one embodiment, the Baume degree of the acid etching waste liquid after impurity removal is 24 Be-30 Be DEG, and the pH value is 1.0-1.5.
In one embodiment, the mesh number of the filter screen for filtering the supernatant is 2500 meshes. Therefore, the method can effectively remove the precipitate and other fine impurities in the solution and improve the filtering and purifying effect.
In one embodiment, the settled sludge of the acid etching waste liquid after settlement and stratification is dissolved by ammonia water to generate cuprammonia, which can be used for reproduction to achieve the effect of recycling. Specifically, when the sediment sludge and the ammonia water are mixed, the ammonia water is firstly added, then the sediment sludge is added, the materials are fed in a crossed manner, and the pH value of the cuprammonia after complete reaction is about 8.8.
And S2, adding soluble magnesium salt into the alkaline etching waste liquid, stirring for reaction, settling and layering, and filtering the supernatant to obtain the alkaline etching waste liquid after impurity removal. It is understood that the soluble magnesium salt is selected from at least one of magnesium chloride, magnesium sulfate, magnesium nitrate, and the like.
Preferably, magnesium chloride is used. Specifically, adding a magnesium chloride hexahydrate solution into the alkaline etching waste liquid, and stirring for reaction for 0.5-2 hours, so that magnesium ions and arsenate ions or arsenite ions react to generate precipitates: 3Mg2++2AsO4 3-＝Mg3(AsO4)2↓、3Mg2++2AsO3 3-＝Mg3(AsO3)2↓. Then standing, settling and layering, taking supernatant fluid, and filtering to obtain the alkaline etching waste liquid without impurities such as arsenic, water insoluble substances and the like.
Furthermore, the ratio of the added weight of the magnesium chloride hexahydrate to the volume of the alkaline etching waste liquid is 2 g/L-2.5 g/L. Specifically, 400Kg of magnesium chloride hexahydrate is added into 4m3 of water, fully and uniformly stirred to prepare a magnesium chloride hexahydrate solution, then 0.5m 3-0.6 m3 of magnesium chloride hexahydrate solution is added into 25m3 of alkaline etching waste liquid, and the mixture is stirred and reacts for 0.5-2 hours.
In one embodiment, the Baume degree of the alkaline etching waste liquid after impurity removal is 12 Be-20 Be degrees, and the pH value is 8.0-9.0.
It is understood that steps S1 and S2 have no explicit order of precedence, and both may be performed simultaneously. If the acidic etching waste liquid or the alkaline etching waste liquid contains solid impurities such as sand and stone, the etching waste liquid is required to be filtered and subjected to impurity removal treatment firstly, so that solid particle impurities such as sand and stone in the etching waste liquid are filtered, the subsequent purification effect and efficiency are improved, and otherwise, the filtering step can be omitted.
And S3, mixing and reacting the impurity-removed acidic etching waste liquid and the impurity-removed alkaline etching waste liquid to obtain the basic copper chloride.
Specifically, the acidic etching waste liquid after the impurity removal in the step S1 and the alkaline etching waste liquid after the impurity removal in the step S2 are respectively preheated to 43-55 ℃, then mixed in the presence of basic copper chloride seed crystals, reacted at the temperature of 68-72 ℃ and at the stirring speed of 65-85 r/min, and then subjected to filter pressing, and the solid is collected to obtain the basic copper chloride.
Further, the addition amount of the basic copper chloride seed crystal is 70Kg/15m3～100Kg/15m3. It can be understood that the ratio of the weight of the basic copper chloride seeds added to the sum of the volumes of the acidic spent etching solution and the alkaline spent etching solution is 70Kg/15m3～100Kg/15m3。
The acid etching waste liquid and the alkaline etching waste liquid are respectively preheated to proper temperatures of 43-55 ℃ before reaction, so that the temperature difference between the raw materials and the crystallization reaction is reduced, the reaction is prevented from being unstable, seed crystals are added to promote the formation of crystals, the proper reaction temperature and stirring speed are controlled, and the generation efficiency of the basic copper chloride and the recovery rate of copper in the etching waste liquid are improved. During the production process, when the stirring speed is adjusted to 90r/min, the particle size of the generated basic copper chloride is smaller than 30 mu m, the basic copper chloride is adhered together and is difficult to wash and filter, and the moisture content of a filter cake is high, so that the industrial production is not facilitated.
In one embodiment, the copper oxychloride seed crystals are added in the form of a dispersion in a filtrate obtained by filtering a saturated aqueous solution of copper oxychloride or a mixed solution containing copper oxychloride.
Specifically, water or basic copper chloride mother liquor is added into a reactor, stirred and heated to 68-72 ℃, and then basic copper chloride seed crystals are added. Wherein the basic copper chloride mother liquor is a filtrate generated by filtering the mixed liquor containing the basic copper chloride in the step S3.
In one embodiment, in the reaction process of the acid etching waste liquid after impurity removal and the alkaline etching waste liquid after impurity removal, the acid etching waste liquid after impurity removal and preheating and the alkaline etching waste liquid after impurity removal and preheating are continuously added, so that the pH value of the acid etching waste liquid and the alkaline etching waste liquid is 4.30-5.00 when the acid etching waste liquid and the alkaline etching waste liquid react.
Further, the flow rate of the acid etching waste liquid after impurity removal and the alkaline etching waste liquid after impurity removal when being added is controlled between 2 cubic per hour and 6 cubic per hour。The flow of the acid etching waste liquid and the alkaline etching waste liquid after impurity removal in the reaction process is strictly controlled, so that the pH value of a reaction system is conveniently adjusted to be maintained between 4.30 and 5.00, the reaction is more sufficient, the production efficiency is improved, and meanwhile, the reaction is promotedThe copper in the etching waste liquid is recycled, and the obtained basic copper chloride has high purity.
And S4, reacting the basic copper chloride obtained in the step S3 with ammonia water to generate a precipitate, filtering to obtain filter residue, purifying by washing water, adding water, and pulping to obtain copper hydroxide slurry.
Specifically, ammonia water with a concentration of 20 wt% is fully reacted with the basic copper chloride prepared in step S3 to generate copper hydroxide: cu2(OH)3Cl+4NH3·H2O→Cu(OH)2↓+[Cu(NH3)4]2+And + Cl-, then performing filter pressing, purifying the obtained filter cake by washing water, and adding tap water for pulping to obtain copper hydroxide slurry.
Further, according to the proportion of 1Kg of basic copper chloride to 1.2L-1.3L of 20 wt% ammonia water, the ammonia water and the basic copper chloride are mixed and reacted. The basic copper chloride is fully converted into copper hydroxide by controlling the proportion of ammonia water and the basic copper chloride, and the filter cake after filter pressing is washed and purified to effectively remove residual chloride ions and ammonia salt in the filter cake.
S5, adding sulfuric acid into the copper hydroxide slurry obtained in the step S4, adjusting the pH value of the copper hydroxide slurry to 0.5-1.0, and performing heat filtration treatment to obtain a mixed solution containing copper sulfate; and cooling and crystallizing the mixed solution containing copper sulfate, performing solid-liquid separation to obtain filter residue and filtrate, and drying the filter residue to obtain copper sulfate.
Specifically, adding 98% by mass of concentrated sulfuric acid into the copper hydroxide slurry for acidification to generate copper sulfate: cu (OH)2+H2SO4＝CuSO4+2H20. And gradually reducing the pH value of the mixed system along with the addition of concentrated sulfuric acid, and completing acidification when the pH value is reduced to 0.5-1.0. Because concentrated sulfuric acid is mixed with copper hydroxide and water for reaction, a large amount of heat is generated, even the solution is locally boiled, and the temperature of a reaction system reaches about 100 ℃ when acidification is finished; then carrying out thermal filter pressing on the reaction system to obtain a mixed solution containing copper sulfate; cooling the mixed solution containing copper sulfate to below 45 deg.C, separating copper sulfate crystal out, performing solid-liquid separation to obtain copper sulfate crystal and filtrate, and drying the copper sulfate crystal to obtain copper sulfate crystalTo copper sulphate product (CuSO)4·5H20) The obtained copper sulfate has low impurity content and reaches the electroplating grade standard.
In one embodiment, the mixed solution containing copper sulfate is cooled, crystallized and filtered, and the filtrate obtained after filtering is recycled to step S5 to replace part of concentrated sulfuric acid to acidify the copper hydroxide slurry. Therefore, the using amount of concentrated sulfuric acid can be effectively saved, the cost is saved, and meanwhile, the pressure and the cost of waste liquid treatment are reduced.
The following are specific examples
Example 1
1. Removing impurities from the acidic etching waste liquid:
5m3 tap water is added into a sodium chlorate preparation tank, then 2 tons of solid sodium chlorate is added, and the mixture is uniformly stirred to prepare a sodium chlorate solution.
And starting an acid etching waste liquid lifting pump, starting filter pressing, overflowing the generated filtrate to an acid etching waste liquid hydraulic filter tank, and lifting the filtrate to an acid etching waste liquid purification tank for purification treatment through a filter pressing tank lifting pump.
Starting the stirrer, and adding a sodium chlorate solution into the acidic etching waste liquid purification tank to remove Cu in the acidic etching waste liquid+、Fe2+Oxidation to Cu2+、Fe3+Judging an oxidation end point according to the color of the acidic etching waste liquid, and when the acidic etching waste liquid is green and transparent, determining the oxidation end point without continuously adding a sodium chloride solution; otherwise, the sodium chloride solution is continuously added until the solution is green and transparent. Adding ammonia water into the purification tank, adjusting the pH value of the acidic etching waste liquid to 1.8, reacting for about 2 hours, and then stopping stirring.
Calculated by the ratio of the weight of the activated carbon to the volume of the acid etching waste liquid, 5Kg/20m3～6Kg/20m3Activated carbon is added into the acidic etching waste liquid purification tank for adsorbing organic impurities such as petroleum and the like. And then standing and settling for about 10 hours, layering the precipitate and the supernatant, filtering the supernatant by a precision filter, and lifting the supernatant to an acid etching waste liquid working tank for later use.
The results of the detection of the acidic etching waste liquid before and after the impurity removal are shown in table 1 below, and the baume degree after the impurity removal is 29Be °.
TABLE 1 index of acidic waste etching solution before and after impurity removal
| Index (I) | pH value | Cu2+(g/L) | Fe(ppm) | Al(ppm) | As(ppm) | Organic impurities |
| Before removing impurities | -1 | 110 | 35 | 7 | 2 | Small amount of |
| After removing impurities | 1.5 | 100 | 20 | 5 | 0.3 | Is free of |
2. Removing impurities from alkaline etching waste liquid
To 25m3Adding 0.1Kg/L magnesium chloride hexahydrate solution of 0.6m into the waste alkaline etching solution3Stirring for about 45 minutes to remove arsenic in the alkaline etching waste liquid, standing for about 10 hours to perform sedimentation and layering, filtering supernatant through a precision filter, and lifting filtrate to an alkaline etching waste liquid working tank for later use.
The results of the detection of the alkaline etching waste liquid before and after the impurity removal are shown in Table 2 below, and the baume degree after the impurity removal is 27Be degrees.
TABLE 2 index of alkaline etching waste liquid before and after impurity removal
| Index (I) | pH value | Cu(g/L) | As(ppm) | Organic impurities |
| Before removing impurities | 8 | 100 | 9 | Small amount of |
| After removing impurities | 8.5 | 90 | 0.1 | Is free of |
3. Production of basic copper chloride by neutralization reaction
1) Seed preparation
Tap water was added to the crystallizer up to the specified point, i.e. just above the steam line in the crystallizer. Starting a crystallizing tank stirrer in the process of pumping tap water into the crystallizing reaction tank, wherein the stirring speed is 75r/min, and opening the self-circulation of the crystallizing tank.
And opening a steam heating valve, raising the temperature of the materials in the crystallization tank to 70 +/-2 ℃, and closing the steam heating valve after the temperature is reached. 80Kg of seed copper oxychloride was added to the crystallizer.
2) Preheating of raw materials
Starting the automatic control device for the acidic etching waste liquid transfusion, feeding the acidic etching waste liquid into the acidic etching waste liquid preheating tank, opening steam, and heating to 45 ℃.
Starting the automatic control device for the alkaline etching waste liquid transfusion, feeding the alkaline etching waste liquid into the preheating tank, opening the steam, and heating to 45 ℃.
3) Production driving
When the temperature of the materials in the crystallization tank reaches 70 +/-2 ℃ and the temperature of the materials in the preheating tank reaches 45 ℃, respectively starting the acid etching waste liquid feeding pump and the alkaline etching waste liquid feeding pump to feed materials into the crystallization tank.
In the process of production start-up, the temperature of reaction crystallization in the crystallization tank is ensured to be 68-72 ℃, and the rotation speed of crystallization stirring is 75 r/min. The feeding amount is gradually increased from small to large, the feeding amount is gradually increased from 1100L/h to 6000L/h, the pH value of the materials in the crystallization tank is reduced from 7 to 4.30-5.0, and the pH value is slowly adjusted until the basic copper chloride is normally produced.
4) When the basic copper chloride is normally produced and the liquid level in the crystallizing tank reaches 30-50 cm away from the top of the tank, pumping the basic copper chloride slurry in the crystallizing tank into a filter press for filter pressing and dehydration, wherein filtrate, namely basic copper chloride mother liquor, flows into a clarifying barrel and overflows into a crystallization mother liquor pool from the clarifying barrel; the filter cake is basic copper chloride.
4. Basic copper chloride-chlorine converter
Transferring the filter-pressed basic copper chloride to an ammonia transfer tank, pumping ammonia water into the tank according to the proportion of 1 ton of alkali type copper chloride to 1.2 square and 20 wt% of ammonia water, and reacting for about 0.5 hour to generate copper hydroxide.
5. Copper hydroxide washing water pulping
Pumping the copper hydroxide in the ammonia converter into a copper hydroxide filter press for filter pressing, discharging the copper hydroxide into a copper hydroxide pulping tank after washing water purification of a filter cake, and adding tap water for pulping to obtain copper hydroxide slurry.
6. Acidification with sulfuric acid
Pumping the slurry in the copper hydroxide pulping tank into an acidification tank, adding 98% concentrated sulfuric acid after pumping, controlling the pH at the end point of acidification to be 0.8 and the temperature to be about 100 ℃, filtering the acidified hot material by using a filter press after acidification is finished, feeding the filtrate into a crystallization tank, opening the crystallization tank to cool by using cooling water, and centrifuging, washing, centrifuging, drying and packaging the slurry after cooling to below 45 ℃ to obtain a copper sulfate product.
7. Detection of
The copper sulfate product obtained by production is detected, and the detection result is shown in the following table 3.
TABLE 3 detection indexes of copper sulfate products
Example 2
Example 2 is essentially the same as example 1 except that the basic copper chloride mother liquor produced in example 1 is used in place of the tap water in example 1.
Example 3
Example 3 is essentially the same as example 2, except for the following:
1) and in the step of removing impurities from the acidic etching waste liquid, ammonia water is added into the purification tank to adjust the pH value of the acidic etching waste liquid to be different, wherein the pH value of the acidic etching waste liquid is 1.8 in example 2, and the pH value of the acidic etching waste liquid is 1.9 in example 3.
2) The raw materials are different, and specifically comprise:
the baume degree of the acidic etching waste liquid before impurity removal is 27Be degrees, the pH value is-0.5, the baume degree after impurity removal is 26Be degrees, and the pH value is 1.5;
the baume degree of the alkaline etching waste liquid before impurity removal is 16Be degrees, the pH value is 10.5, the baume degree after impurity removal is 15Be degrees, and the pH value is 9.0.
3) The preheating temperature is different, and specifically comprises the following steps: the preheating temperature for example 2 was 45 ℃ and the preheating temperature for example 3 was 48 ℃.
Example 4
Example 4 is essentially the same as example 2, except for the following:
1) and in the step of removing impurities from the acidic etching waste liquid, ammonia water is added into the purification tank to adjust the pH value of the acidic etching waste liquid to be different, wherein the pH value of the acidic etching waste liquid is 1.8 in example 2, and the pH value of the acidic etching waste liquid is 1.7 in example 4.
2) The raw materials are different, and specifically comprise:
the baume degree of the acidic etching waste liquid before impurity removal is 25Be degrees, the pH value is-0.8, the baume degree after impurity removal is 24Be degrees, and the pH value is 1.2;
the baume degree of the alkaline etching waste liquid before impurity removal is 13Be degrees, the pH value is 9, the baume degree after impurity removal is 12Be degrees, and the pH value is 8.5.
3) The preheating temperature is different, and specifically comprises the following steps: the preheating temperature in example 2 was 45 ℃ and the preheating temperature in example 4 was 55 ℃.
Sampling detection is carried out on the copper sulfate products obtained in the embodiments 2 to 4, and according to the statistical analysis of the detection results, the quality of the copper sulfate products obtained in the embodiments 2 to 4 meets the standard of the following table 4, and all the copper sulfate products meet the requirement of electroplating-grade copper sulfate.
TABLE 4 copper sulfate product detection indexes
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that the pH of the acidic etching waste liquid is adjusted to 1.8 and the pH of the acidic etching waste liquid is adjusted to 1.2 in example 1 in which the pH of the acidic etching waste liquid is adjusted to a different pH from that of the copper hydroxide slurry by adding ammonia water to the purification tank. Example 1 the pH of the copper hydroxide slurry was adjusted to 0.8 and comparative example 1 the pH of the copper hydroxide slurry was adjusted to 1.5.
The results of the tests on the copper sulfate product obtained from the production are shown in Table 5 below.
TABLE 5 detection indexes of comparative example 1 copper sulfate product
As can be seen from Table 5 above, the copper sulfate product produced in comparative example 1 did not meet the plating grade standards.
Comparative example 2
Comparative example 2 is substantially the same as example 2 except for the following:
1) different reagents are added in the step 4 in the reaction with the basic copper chloride, 20 wt% of ammonia water is added in the example 2, 20 wt% of sodium hydroxide solution is added in the comparative example 2, correspondingly, the precipitate generated after the reaction is about 0.5 hour is different, the blue flocculent copper hydroxide precipitate is obtained in the example 2, and the brown black flaky copper oxide precipitate is obtained in the comparative example 2.
2) Step 5 copper oxide washing and pulping operations were the same as in example 2 except that the operation target in example 2 was copper hydroxide and the operation target in comparative example 2 was copper oxide, and copper oxide slurry was obtained.
3) The operation of sulfuric acid acidification in step 6 is the same as that of example 2 except that the object of sulfuric acid acidification in example 2 is copper hydroxide and the object of acidification in comparative example 2 is copper oxide.
The results of the tests on the copper sulfate product obtained from the production are shown in Table 6 below.
TABLE 6 detection indexes of copper sulfate product of comparative example 2
In operation, it was found that since the copper oxide in comparative example 2 was precipitated in a flake form, both the filtration separation and the washing water purification were difficult.
As can be seen from Table 6 above, the copper sulfate product of comparative example 2 did not meet the plating level standards, especially the chloride content was well above the plating level standards.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The production method of copper sulfate is characterized by comprising the following steps:
adding an oxidant into the acidic etching waste liquid to oxidize cuprous ions and ferrous ions in the acidic etching waste liquid, then adjusting the pH value to 1.7-1.9, stirring for reaction, adding activated carbon, settling and layering, and then taking supernatant for filtering treatment to obtain the impurity-removed acidic etching waste liquid;
adding soluble magnesium salt into the alkaline etching waste liquid for reaction, taking supernatant fluid for filtration treatment after sedimentation and layering to obtain the alkaline etching waste liquid after impurity removal;
respectively preheating the acid etching waste liquid after impurity removal and the alkaline etching waste liquid after impurity removal to 43-55 ℃, and then mixing and reacting in the presence of basic copper chloride seed crystals to obtain the basic copper chloride;
reacting the basic copper chloride with ammonia water to generate a precipitate, filtering to obtain filter residue, purifying by washing water, adding water, and pulping to obtain copper hydroxide slurry;
adding sulfuric acid into the copper hydroxide slurry, adjusting the pH value of the copper hydroxide slurry to 0.5-1.0, and performing heat filtration treatment to obtain a mixed solution containing copper sulfate; and (3) cooling and crystallizing the mixed solution containing copper sulfate, performing solid-liquid separation to obtain copper sulfate crystals, and drying.
2. The method for producing copper sulfate as claimed in claim 1, wherein the reagent for adjusting the pH to 1.7 to 1.9 is ammonia water.
3. The method for producing copper sulfate as claimed in claim 1, wherein the mass-to-volume ratio of the activated carbon to the acidic etching waste liquid is (0.2 to 0.3) g: 1L.
4. The method for producing copper sulfate as claimed in claim 1, wherein the baume degree of the acidic etching waste liquid after impurity removal is 24Be ° to 30Be °, and the pH value is 1.0 to 1.5.
5. The method for producing copper sulfate as claimed in claim 1, wherein the baume degree of the alkaline etching waste liquid after impurity removal is 12Be ° to 20Be °, and the pH value is 8.0 to 9.0.
6. The method for producing copper sulfate as claimed in any one of claims 1 to 5, wherein in the step of reacting the copper oxychloride with aqueous ammonia to form a precipitate, the concentration of the aqueous ammonia used is 20 wt%, and the volume weight ratio of the aqueous ammonia to the copper oxychloride is (1.2-1.3) L:1 Kg.
7. The method for producing copper sulfate as claimed in any one of claims 1 to 5, wherein the concentration of sulfuric acid is 98 wt% or more.
8. The method for producing copper sulfate according to any one of claims 1 to 5, wherein the mixing reaction of the impurity-removed acidic etching waste liquid and the impurity-removed alkaline etching waste liquid in the presence of basic copper chloride seed crystals is carried out at a temperature of 68 ℃ to 72 ℃ and a stirring speed of 65r/min to 85 r/min.
9. The method for producing copper sulfate as claimed in claim 8, wherein the acidic etching waste solution after impurity removal and the alkaline etching waste solution after impurity removal are continuously added during the reaction process, so that the pH value of the acidic etching waste solution and the alkaline etching waste solution is 4.30-5.00 during the reaction.
10. The method for producing copper sulfate as claimed in claim 9, wherein the flow rate of the continuously fed preheated acidic etching waste liquid and preheated alkaline etching waste liquid is controlled to 2 to 6 cubic/hr.
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| CN109534384B (en) * | 2019-01-24 | 2020-12-25 | 苏州华锋环保技术有限公司 | High-purity copper sulfate production line |
| CN110158089A (en) * | 2019-05-29 | 2019-08-23 | 惠州大亚湾亿田环保技术有限公司 | The alkalinity erosion copper waste liquor recovery process method of zero-emission |
| CN111908498A (en) * | 2019-12-27 | 2020-11-10 | 深圳市宝安东江环保技术有限公司 | Method for producing copper oxide by using printed circuit board etching waste liquid and electric suction filtration device |
| CN111847496A (en) * | 2020-06-23 | 2020-10-30 | 吴江市威士达铜业科技有限公司 | Preparation method of stable-state copper hydroxide |
| CN111943423A (en) * | 2020-07-10 | 2020-11-17 | 山东东顺环保科技有限公司 | Method and system for treating acidic copper-containing etching liquid |
| CN112850778A (en) * | 2020-11-19 | 2021-05-28 | 吴江市威士达铜业科技有限公司 | Preparation method of basic copper chloride |
| CN114684847B (en) * | 2020-12-25 | 2023-11-10 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
| CN112813489B (en) * | 2020-12-30 | 2022-04-29 | 广东臻鼎环境科技有限公司 | Preparation method of reagent-grade copper chloride dihydrate crystal |
| CN114031105B (en) * | 2021-11-30 | 2022-11-29 | 中南大学 | Treatment method of copper-containing etching waste liquid |
| US11939229B2 (en) * | 2021-11-30 | 2024-03-26 | Central South University | Method for treating copper-containing waste etching solution |
| CN114195315A (en) * | 2021-12-30 | 2022-03-18 | 江苏维达环保科技有限公司 | Method for combined treatment of acidic and non-acidic copper-containing etching waste liquid, tin stripping waste liquid and copper nitrate waste liquid |
| CN114314637A (en) * | 2021-12-31 | 2022-04-12 | 东江环保股份有限公司 | Method for preparing high-purity copper sulfate from acidic copper chloride etching waste liquid |
| WO2023123362A1 (en) * | 2021-12-31 | 2023-07-06 | 东江环保股份有限公司 | Method for preparing high-purity copper sulfate from acidic copper chloride etching waste liquid |
| CN114702058A (en) * | 2022-04-25 | 2022-07-05 | 惠州市东江环保技术有限公司 | Process for comprehensively recycling micro-etching waste liquid |
| CN117247124A (en) * | 2023-11-10 | 2023-12-19 | 中山火炬环保新材料有限公司 | Intelligent treatment method and treatment system for copper-containing etching waste liquid |
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| CN103693672B (en) * | 2013-12-25 | 2015-08-26 | 广州科城环保科技有限公司 | A kind of cupric acid waste liquid not containing ammonia nitrogen prepares the method for plating level cupric sulfate pentahydrate |
| CN105129838A (en) * | 2015-07-02 | 2015-12-09 | 清远市新绿环境技术有限公司 | Method for producing copper sulphate by using copper-containing waste solution of PCB circuit board plant |
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