CN112978786A - Method and system for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate - Google Patents
Method and system for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate Download PDFInfo
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Abstract
The invention discloses a method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate, which comprises the following steps: step 1, washing with water; step 2, acid washing; step 3, preparing a first mother liquor; step 4, crystallizing; step 5, settling; step 6, preparing a wet product; and 7, drying to obtain a finished product. The method uses pure water and an acid solution saturated with copper ions to sequentially wash and refine the crude basic copper carbonate to remove most impurities, uses a saturated copper sulfate solution to wash copper sulfate pentahydrate crystals to improve the grade of the copper sulfate pentahydrate, is matched with a copper sulfate mother liquor calcium removal process, can maintain the production continuity, greatly improves the recycling frequency of the copper sulfate mother liquor, reduces the waste liquor treatment cost during production, solves the problems of high cost, complex process flow and large waste liquor discharge amount in the existing preparation method of the electroplating-grade copper sulfate pentahydrate, realizes the technical effects of high recycling frequency use of the mother liquor and continuous crystallization, and ensures the requirement of producing the electroplating-grade copper sulfate pentahydrate.
Description
Technical Field
The invention relates to the field of preparation of copper sulfate pentahydrate, in particular to a method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate.
Background
Printed Circuit Boards (PCBs) are becoming increasingly dense, greatly reducing the dimensions of the traces, pads and vias on the Circuit Board. In the field of high-end PCB manufacturing, a subtractive Process (subtractive) is gradually replaced by common Semi-Additive SAP (Semi-Additive Process) and improved Semi-Additive m-SAP (Modified Semi-Additive Process). The key feature of such PCBs is that the Line-to-Line spacing (Line/Space) of the copper wires is small, for example, in the mature m-SAP process, the Line-to-Line spacing L/S of the copper wires is 30 μm/30 μm, and in such a size, any pin hole and copper slag defect caused by the copper electroplating process will cause scrap. Therefore, there is an urgent need for a highly reliable copper electroplating process, which is realized on the basis of a high-purity raw material. The main raw materials of the printed circuit board copper electroplating process are copper sulfate pentahydrate, sulfuric acid and additives.
Wang et al, in patent application No. 201810780164.9 entitled method for producing copper sulfate of electroplating grade from copper-containing sludge, disclose a method for producing copper sulfate pentahydrate of electroplating grade from copper-containing sludge as a copper source. Dissolving the copper-containing sludge by acid, removing impurities to prepare a clean copper-containing acidic solution, extracting copper ions to an organic phase by using an organic extractant, performing back extraction to prepare a copper sulfate solution from the copper ions, and finally concentrating and crystallizing to obtain the electroplating-grade copper sulfate pentahydrate. However, the method has the defects of complex preparation process and higher cost.
Tanzea et al, in patent application No. 201210588188.7 entitled method for preparing electronic grade high purity copper sulfate pentahydrate, disclose another method for preparing electroplating grade copper sulfate pentahydrate, which still uses an extraction process to prepare copper sulfate pentahydrate from a copper sulfate solution, but uses a copper source of technical grade copper sulfate pentahydrate, and further discloses an extractant different from that disclosed in Wangwu et al. The method uses industrial-grade copper sulfate pentahydrate as a raw material, so that the cost is high.
Fungine et al disclose another process for making electroplated grade copper sulfate pentahydrate in patent application No. 201711134811.0 entitled Process for making electroplated grade copper sulfate. The copper source used in the method is acid copper waste liquid. Adsorbing the waste liquid with resin to eliminate organic matter additive, adsorbing copper ion with selective copper ion adsorbing resin, desorbing copper ion with ion exchange process to prepare copper containing solution, purifying the copper containing solution, evaporating and crystallizing to obtain blue vitriol. The method has the defects that the resin adsorption and evaporative crystallization processes are adopted, the process is long in time consumption, and a large amount of energy and water are consumed.
Therefore, it is urgently needed to develop a method for preparing electroplating-grade copper sulfate pentahydrate at lower cost, which is used for meeting the preparation requirement of high-density printed circuit boards for the copper sulfate pentahydrate.
Disclosure of Invention
The invention aims to provide a method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate. According to one aspect of the invention, the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate comprises the following steps:
step 3, injecting pure water or copper sulfate mother liquor into a reaction kettle, adding the refined basic copper carbonate into the reaction kettle while stirring, after uniformly mixing, adjusting the temperature in the reaction kettle, slowly adding concentrated sulfuric acid, and obtaining first mother liquor after the reaction is finished;
step 6, injecting a saturated copper sulfate solution into the second centrifugal machine, uniformly stirring, performing fourth centrifugation, performing solid-liquid separation, and discharging an upper third solution to obtain an electroplating-grade wet copper sulfate pentahydrate product;
and 7, drying the electroplating-grade copper sulfate pentahydrate wet product to obtain the electroplating-grade copper sulfate pentahydrate.
The invention has the beneficial effects that: the method uses the combined washing operation of pure water and the saturated acid solution containing copper ions to refine the crude basic copper carbonate to remove most of water-soluble and water-insoluble impurities, and the saturated copper sulfate solution is combined to wash the blue copperas crystal, so that the blue copperas grade can be greatly improved, meanwhile, the independent copper sulfate mother liquor calcium removal process is matched, the production continuity can be maintained, the recycling frequency of the copper sulfate mother liquor is greatly improved, the waste liquid treatment cost during production is reduced, the product meets the HG-T3592-2010 high-quality standard, the problems of high cost, complex process flow and large waste liquid discharge amount in the existing electroplating-grade copper sulfate pentahydrate preparation method are solved, the technical effects of high recycling frequency use of the mother liquor and continuous crystallization are realized, and the impurity content of the product copper sulfate pentahydrate meets the national standard requirement by using a relatively simple process.
In some embodiments, in step 5, the second mother liquor is extracted into a temporary storage tank for storage, sampling analysis is performed on the calcium ion concentration in the second mother liquor in the temporary storage tank, and when the calcium ion concentration is greater than the calcium saturation concentration, the second mother liquor is calcium saturated mother liquor, and calcium removal treatment is performed on the second mother liquor; when the calcium ion concentration is less than the calcium saturation concentration, the second mother liquor is used as a copper sulfate mother liquor in the step 3, and the calcium saturation concentration is 500 ppm. By analyzing the calcium ion concentration and removing calcium from the second mother liquor, the calcium ion impurities brought into the reaction kettle when the second mother liquor is used as copper sulfate mother liquor for circulation can be reduced. In the case of acidic pH, only calcium ions in the reaction system form slightly soluble calcium sulfate. When the concentration of calcium ions in the copper sulfate mother liquor is higher than 500ppm, newly introduced calcium in a reaction system cannot be dissolved, calcium sulfate precipitation is directly formed, insoluble impurities in the first mother liquor are increased, and the quality of the final copper sulfate pentahydrate is affected.
In some embodiments, the calcium removal treatment is to replace part of the second mother liquor with pure water or clean mother liquor, transfer the replaced part of the second mother liquor as the mother liquor to be calcium removed into a calcium removal tank, adjust the pH value of the mother liquor to be calcium removed with an alkaline liquid, add a calcium remover under stirring, keep standing after stirring for 30min, obtain a mother liquor after calcium removal, filter the mother liquor after calcium removal through a microfiltration device, obtain clean mother liquor, and use the clean mother liquor as a copper sulfate mother liquor in step 3. The mother liquor to be decalcified is treated by the decalcifying agent, calcium ions in the mother liquor to be decalcified generate calcium precipitates through reaction, then the mother liquor after the decalcification is filtered by the microfiltration device, the calcium precipitates are separated from the mother liquor after the decalcification, clean mother liquor is obtained, and the concentration of the calcium ions in the clean mother liquor can be reduced. And the second mother liquor is recycled.
In some embodiments, the mass ratio of pure water to crude basic copper carbonate in step 1 is from 0.5:1 to 5: 1. The crude basic copper carbonate can contain more NaCl and NaClO according to different raw materials or processes for preparation3、Na2CO3、NaHCO3And water-soluble impurities such as metal carbonates and hydroxides which are hardly soluble in water. When the mass ratio of the pure water to the crude basic copper carbonate is lower than 0.5:1, the removal of soluble impurities in the powdery crude basic copper carbonate is not facilitated; when the mass ratio of pure water to crude basic copper carbonate is higher than 5:1, the total content of soluble impurities in the crude basic copper carbonate is 1 wt%In addition, excessive addition of pure water does not bring about more sufficient washing and causes unnecessary waste.
In some embodiments, the mass ratio of the copper ion-saturated acidic solution to the crude basic copper carbonate in step 2 is 1: 2. The second washing with the acid solution saturated with copper ions can make up the defect that the pure water washing can not remove insoluble impurities in the crude basic copper carbonate. The second washing is intended to remove as much as possible the water remaining on the surface of the first water-washed object while dissolving and removing part of the insoluble impurities.
In some embodiments, the pH of the copper ion-saturated acidic solution is from 0.1 to 4.0, and the ionic composition of the copper ion-saturated acidic solution is Cu2+And M2-The copper ion saturated acidic solution is prepared by dissolving soluble copper salt CuM in pure water and dissolving in acidic solution H2M is used for adjusting the pH value to obtain the compound. In order to inhibit the dissolution of the first water-washed material, i.e. crude basic copper carbonate, by acid in the second washing process, an acidic solution saturated with copper ions is selected as the washing solution. According to the metal ion precipitation conditions, most of metal ions in the acidic solution with the pH value of below 4.0 are in a free state which can be completely mixed with the acidic solution, and in the state, the metal ions can be separated from the basic copper carbonate solid by a filtration method, so that the purpose of dissolving and removing insoluble impurities is achieved.
In some embodiments, the saturated copper sulfate solution has a calcium ion content of less than 200ppm and a chloride ion concentration of less than 800 ppm. And saturated copper sulfate solution is injected into the second centrifugal machine to wash the copper sulfate pentahydrate crystals, so that a small amount of second mother liquor remained on the surfaces of the copper sulfate pentahydrate crystals is cleaned, and the impurity content in finished products is reduced. When the content of calcium ions in the saturated copper sulfate solution is more than 200ppm or the concentration of chloride ions is more than 800ppm, the saturated copper sulfate solution cannot achieve the purpose of washing the copper sulfate pentahydrate crystals, but impurities such as calcium ions, chloride ions and the like are brought to the surfaces of the copper sulfate pentahydrate crystals, so that the quality of products is influenced.
In some embodiments, the mass ratio of the refined basic copper carbonate to the concentrated sulfuric acid in step 3 is: 2:1-2:1.3, the temperature of the first mother liquor in the step 3 is 55-85 ℃, and the concentration of copper ions in the first mother liquor in the step 3 is 140 g/L. When the mass ratio of the refined basic copper carbonate to the concentrated sulfuric acid is lower than 2:1, the pH value of the copper sulfate mother liquor obtained by the reaction is higher, and partial insoluble impurities are left; when the mass ratio of the refined basic copper carbonate to the concentrated sulfuric acid is higher than 2:1.3, the concentrated sulfuric acid is wasted, ice water is wasted due to overhigh temperature, and the subsequent cooling crystallization time is long, so that the yield is influenced. When the concentration of copper ions in the first mother liquor is lower than 130g/L, the reaction efficiency is lower; when the concentration of copper ions is higher than 140g/L, copper sulfate pentahydrate crystals can be separated out too quickly, so that part of basic copper carbonate is wrapped by the copper sulfate pentahydrate crystals, and electroplating-grade copper sulfate pentahydrate cannot be obtained.
In some embodiments, the mass ratio of the saturated copper sulfate solution injected in step 6 to the copper sulfate pentahydrate crystals is: 0.5:1-5:1, the concentration of copper ions in the saturated copper sulfate solution is 70-80g/L, and the pH value of the saturated copper sulfate solution is 0.1-3.0.
In some embodiments, the settling tank comprises a tank body, a circulating pump and an acid-proof pump, wherein the circulating pump is provided with a first suction inlet which is positioned at the bottom of the tank body, the acid-proof pump is provided with a second suction inlet, and the distance between the second suction inlet and the bottom of the tank body is 15% -50% of the height of the tank body. The circulating pump sets up in the subsider cell body bottom, and the circulating pump is equipped with first suction inlet, and first suction inlet is located the cell body bottom, and the circulating pump of being convenient for will subside in the second centrifuge is gone into to the blue vitriol crystallization pump of cell body bottom. The distance between the suction inlet of the acid-proof pump and the bottom of the tank body is 15% -50% of the height of the tank body, so that the second mother liquor on the upper part of the settling tank can be pumped into the temporary storage tank through the acid-proof pump for storage, calcium ion concentration analysis is carried out on the second mother liquor, and whether calcium removal treatment is needed or not is conveniently judged when the second mother liquor is reused as copper sulfate mother liquor.
Drawings
FIG. 1 is a schematic block diagram of a process for the preparation of electroplating grade copper sulfate pentahydrate from crude basic copper carbonate according to one embodiment of the present invention.
FIG. 2 is a schematic block diagram of the calcium removal treatment process of the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate according to one embodiment of the invention.
Fig. 3 is a schematic structural diagram of a second suction inlet of a settling tank of the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate according to one embodiment of the invention.
Fig. 4 is a top view of a settler of a process for producing electroplating grade copper sulfate pentahydrate from crude basic copper carbonate in accordance with one embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
In this example, copper sulfate was selected from analytically pure copper sulfate supplied from national chemical group chemical reagent Co., Ltd, copper nitrate was selected from analytically pure copper nitrate supplied from national chemical group chemical reagent Co., Ltd, copper chloride was selected from analytically pure copper chloride supplied from national chemical reagent Co., Ltd, copper formate was selected from analytically pure copper formate supplied from national chemical reagent Co., Ltd, copper acetate was selected from analytically pure copper acetate supplied from national chemical reagent Co., Ltd, copper propionate was selected from analytically pure copper propionate supplied from national chemical reagent Co., Ltd, concentrated sulfuric acid was selected from analytically pure concentrated sulfuric acid supplied from national chemical reagent Co., Ltd, nitric acid was selected from analytically pure nitric acid supplied from national chemical reagent Co., Ltd, hydrochloric acid was selected from analytically pure hydrochloric acid supplied from national chemical reagent Co., Ltd, formic acid was selected from analytically pure formic acid supplied from national chemical reagent Co., Ltd, the acetic acid is analytically pure acetic acid supplied by national drug group chemical reagent company, the propionic acid is analytically pure propionic acid supplied by national drug group chemical reagent company, the sodium fluoride is analytically pure sodium fluoride supplied by national drug group chemical reagent company, and the potassium fluoride is analytically pure potassium fluoride supplied by national drug group chemical reagent company;
in this embodiment, the reaction kettle is a stainless steel electric heating reaction kettle supplied by lazhou city permangguan chemical machinery co.ltd, the calcium concentration analysis sampling unit is a calcium and magnesium ion online detection analyzer supplied by shanghai cereal industrial instruments co.ltd, the calcium precipitate microfiltration unit is a tubular ultrafiltration system with a 0.10 μm filter membrane, the temporary storage tank, the settling tank, the crystallization tank and the calcium removal tank are all PP chemical tanks supplied by the usual state creation environmental protection technology co.ltd, and the centrifuge is an S450 type acid and corrosion resistant centrifuge supplied by zhang city yue electromechanical equipment factory.
The reagents and apparatus of this example 1 were used in the following examples 2 to 6.
Example 2
Referring to fig. 1 to 4, the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate comprises the following steps:
and 2, dissolving excessive copper chloride in pure water to prepare a copper ion saturated solution, dropwise adding hydrochloric acid into the copper ion saturated solution, and adjusting the pH value to 2.0 to prepare an acid solution saturated with copper ions. Injecting 2.5kg of copper ion saturated acid solution into a centrifuge, continuously stirring at the rotating speed of 100rpm for 20min, then carrying out secondary centrifugation at the rotating speed of 1000rpm for 10min for solid-liquid separation, then discharging the upper layer of second solution, discharging, finishing refining of crude basic copper carbonate to obtain refined basic copper carbonate, wherein the copper content in the refined basic copper carbonate is 51%;
and 3, injecting 35L of pure water into the reaction kettle, adding 5kg of refined basic copper carbonate into the reaction kettle while stirring, uniformly mixing, adjusting the temperature in the reaction kettle to ensure that the temperature in the reaction kettle is 30 ℃, slowly adding 2.5L of concentrated sulfuric acid, controlling the adding rate of the concentrated sulfuric acid to be 200ml/min, and discharging a large amount of bubbles from a reaction system in the mixing process. After the addition of concentrated sulfuric acid is finished, obtaining a first mother liquor, wherein the first mother liquor is supersaturated copper sulfate mother liquor, is in a dark blue transparent state, and has the temperature of 55 ℃ and the concentration of copper ions of 133 g/L;
and 5, transferring the first mixture into a settling tank 1, settling for 10min, precipitating the copper sulfate pentahydrate crystals to the bottom of the settling tank 1, starting a circulating pump to pump the mixed solution with higher content of the copper sulfate pentahydrate crystals at the bottom of the settling tank 1 to a second centrifugal machine through a first suction port 11, performing third centrifugation, performing solid-liquid separation, and discharging the upper-layer copper sulfate solution to obtain the copper sulfate pentahydrate crystals. The acid-proof pump is provided with a second suction inlet 12, and the distance between the second suction inlet 12 and the bottom of the tank body of the settling tank 1 is 15% of the height of the tank body.
And the copper sulfate solution at the upper part in the settling tank 1 is a second mother solution, and after the copper sulfate pentahydrate crystals in the settling tank are lower than the height of the second suction inlet 12, an acid-resistant pump is started to pump the second mother solution out to the temporary storage tank 2 for temporary storage.
Sampling, analyzing and detecting the calcium ion concentration of the second mother liquor in the temporary storage tank 2 by a calcium concentration analyzing and sampling unit 5, determining that the calcium ion concentration of the second mother liquor in the temporary storage tank 2 is 428ppm and is less than 500ppm of calcium saturation concentration, wherein the second mother liquor can be used as copper sulfate mother liquor for the copper sulfate mother liquor in the step 3 of the next preparation operation;
and 6, injecting a saturated copper sulfate solution into the second centrifugal machine, uniformly stirring, centrifuging for the fourth time, and carrying out solid-liquid separation to obtain the electroplating-grade wet copper sulfate pentahydrate. The mass ratio of the injected saturated copper sulfate solution to the copper sulfate pentahydrate crystal is as follows: 0.5:1, the concentration of copper ions in the saturated copper sulfate solution is 80g/L, the pH value is 3.0, the concentration of calcium ions is 22ppm, and the content of chloride ions is 7 ppm. And discharging the upper layer third solution into a saturated copper sulfate solution tank for storage, wherein when the content of calcium ions in the saturated copper sulfate solution in the tank is less than 200ppm and the concentration of chloride ions is less than 800ppm, the saturated copper sulfate solution can be recycled.
And 7, drying the electroplating-grade copper sulfate pentahydrate wet product at 40 ℃ to obtain electroplating-grade copper sulfate pentahydrate, and analyzing the impurity content of the prepared electroplating-grade copper sulfate pentahydrate, wherein the sum of the metal impurities except calcium in the electroplating-grade copper sulfate pentahydrate is less than 5ppm, the sum of the metal impurity contents is less than 5ppm, and the chlorine impurity content is less than 20 ppm. The content of metal impurities is analyzed by an ICP-OES method, the detection limit is 0.0003%, the content of chloride ions is analyzed by a UV-Vis method, the detection limit is 0.0010%, and the specific detection results are shown in the following table:
example 3
Referring to fig. 1-4, the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate comprises the following steps:
and 2, dissolving excessive copper nitrate in pure water to prepare a copper ion saturated solution, dropwise adding nitric acid into the copper ion saturated solution, and adjusting the pH value to be 0.1 to prepare an acid solution saturated with copper ions. 2.5kg of copper ion saturated acid solution is injected into a centrifuge, after continuous stirring is carried out for 30min at the rotating speed of 100rpm, secondary centrifugation is carried out, the rotating speed is 1000rpm, the centrifugation time is 10min, solid-liquid separation is carried out, then the second solution on the upper layer is discharged and discharged, the refining of crude basic copper carbonate is finished, refined basic copper carbonate is obtained, and the copper content in the refined basic copper carbonate is 51%;
and 3, injecting 35L of copper sulfate mother liquor into the reaction kettle, wherein the concentration of copper ions in the copper sulfate mother liquor is 70g/L, the pH value is 1.50, the calcium content is 291ppm, and the chlorine content is 848ppm, adding 5kg of refined basic copper carbonate into the reaction kettle while stirring, uniformly mixing, adjusting the temperature in the reaction kettle to ensure that the temperature in the reaction kettle is 30 ℃, slowly adding 3.25L of concentrated sulfuric acid, controlling the adding rate of the concentrated sulfuric acid to be 200ml/min, and discharging a large amount of bubbles in a reaction system in the mixing process. After the addition of concentrated sulfuric acid is finished, obtaining a first mother liquor, wherein the first mother liquor is supersaturated copper sulfate mother liquor, is in a dark blue transparent state, and has the temperature of 64 ℃ and the concentration of copper ions of 137 g/L;
and 5, transferring the first mixture into a settling tank 1, settling for 30min, precipitating the copper sulfate pentahydrate crystals to the bottom of the settling tank 1, starting a circulating pump to pump the mixed solution with higher content of the copper sulfate pentahydrate crystals at the bottom of the settling tank 1 to a second centrifugal machine through a first suction port 11, performing third centrifugation, performing solid-liquid separation, and discharging the upper-layer copper sulfate solution to obtain the copper sulfate pentahydrate crystals. The acid-proof pump is provided with a second suction inlet 12, and the distance between the second suction inlet 12 and the bottom of the tank body of the settling tank 1 is 50% of the height of the tank body.
And the copper sulfate solution at the upper part in the settling tank 1 is a second mother solution, and after the copper sulfate pentahydrate crystals in the settling tank are lower than the height of the second suction inlet 12, an acid-resistant pump is started to pump the second mother solution out to the temporary storage tank 2 for temporary storage.
Sampling, analyzing and detecting the calcium ion concentration of the second mother liquor in the temporary storage tank 2 by a calcium concentration analyzing and sampling unit 5, determining that the calcium ion concentration of the second mother liquor in the temporary storage tank 2 is 380ppm and is less than 500ppm of calcium saturation concentration, wherein the second mother liquor can be used as copper sulfate mother liquor for the copper sulfate mother liquor in the step 3 of the next preparation operation;
and 6, injecting a saturated copper sulfate solution into the second centrifugal machine, uniformly stirring, centrifuging for the fourth time, and carrying out solid-liquid separation to obtain the electroplating-grade wet copper sulfate pentahydrate. The mass ratio of the injected saturated copper sulfate solution to the copper sulfate pentahydrate crystal is as follows: 1:1, the concentration of copper ions in the saturated copper sulfate solution is 70g/L, the pH value is 0.1, the concentration of calcium ions is 22ppm, and the content of chloride ions is 7 ppm. And discharging the upper layer third solution into a saturated copper sulfate solution tank for storage, wherein when the content of calcium ions in the saturated copper sulfate solution in the tank is less than 200ppm and the concentration of chloride ions is less than 800ppm, the saturated copper sulfate solution can be recycled.
And 7, drying the electroplating-grade copper sulfate pentahydrate wet product at 40 ℃ to obtain electroplating-grade copper sulfate pentahydrate, and analyzing the impurity content of the prepared electroplating-grade copper sulfate pentahydrate, wherein the sum of the metal impurities except calcium in the electroplating-grade copper sulfate pentahydrate is less than 5ppm, the sum of the metal impurity contents is less than 5ppm, and the chlorine impurity content is less than 20 ppm. The content of metal impurities is analyzed by an ICP-OES method, the detection limit is 0.0003%, the content of chloride ions is analyzed by a UV-Vis method, the detection limit is 0.0010%, and the specific detection results are shown in the following table:
example 4
Referring to fig. 1 to 4, the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate comprises the following steps:
and 2, dissolving excessive copper formate in pure water to prepare a copper ion saturated solution, dropwise adding formic acid into the copper ion saturated solution, and adjusting the pH value to be 4.0 to prepare an acid solution saturated by copper ions. 2.5kg of copper ion saturated acid solution is injected into a centrifuge, after continuous stirring is carried out for 30min at the rotating speed of 100rpm, secondary centrifugation is carried out, the rotating speed is 1000rpm, the centrifugation time is 10min, solid-liquid separation is carried out, then the second solution on the upper layer is discharged and discharged, the refining of crude basic copper carbonate is finished, refined basic copper carbonate is obtained, and the copper content in the refined basic copper carbonate is 51%;
and 3, injecting 35L of copper sulfate mother liquor into the reaction kettle, wherein the concentration of copper ions in the copper sulfate mother liquor is 75g/L, the pH value is 1.50, the calcium content is 291ppm, and the chlorine content is 848ppm, adding 5kg of refined basic copper carbonate into the reaction kettle while stirring, uniformly mixing, adjusting the temperature in the reaction kettle to ensure that the temperature in the reaction kettle is 30 ℃, slowly adding 3.25L of concentrated sulfuric acid, controlling the adding rate of the concentrated sulfuric acid to be 200ml/min, and discharging a large amount of bubbles in a reaction system in the mixing process. After the addition of concentrated sulfuric acid is finished, obtaining a first mother liquor, wherein the first mother liquor is supersaturated copper sulfate mother liquor, is in a dark blue transparent state, and has the temperature of 85 ℃ and the concentration of copper ions of 135 g/L;
and 5, transferring the first mixture into a settling tank 1, settling for 30min, precipitating the copper sulfate pentahydrate crystals to the bottom of the settling tank 1, starting a circulating pump to pump the mixed solution with higher content of the copper sulfate pentahydrate crystals at the bottom of the settling tank 1 to a second centrifugal machine through a first suction port 11, performing third centrifugation, performing solid-liquid separation, and discharging the upper-layer copper sulfate solution to obtain the copper sulfate pentahydrate crystals. The acid-proof pump is provided with a second suction inlet 12, and the distance between the second suction inlet 12 and the bottom of the tank body of the settling tank 1 is 30% of the height of the tank body.
The copper sulfate solution at the upper part in the settling tank 1 is a second mother solution, and after the copper sulfate pentahydrate crystals in the settling tank are lower than the height of the second suction inlet 12, the acid-resistant pump is started to pump the second mother solution, namely the copper sulfate solution at the upper layer out to the temporary storage tank 2 for temporary storage.
Through calcium concentration analysis sampling unit 5, carry out sample analysis and detection to the calcium ion concentration of second mother liquor in the groove 2 of keeping in, the calcium ion concentration is 530ppm in the second mother liquor in the groove 2 of survey keeping in, is greater than calcium saturated concentration 500ppm, carries out the decalcification to the second mother liquor in the groove 2 of keeping in.
Adding potassium fluoride and potassium hydroxide into water to prepare a calcium remover, replacing one third volume of second mother liquor in the temporary storage tank 2 with clean mother liquor, transferring the replaced second mother liquor serving as the mother liquor to be subjected to calcium removal into a calcium removal tank 3, adjusting the pH value of the calcium removal mother liquor in the calcium removal tank 3 to be 3.5 with potassium hydroxide, adding the calcium remover in a stirring state, continuously stirring for 30min, standing for 3 hours to obtain the mother liquor subjected to calcium removal, and filtering the mother liquor subjected to calcium removal by a microfiltration device, namely a calcium precipitate microfiltration unit 4 to obtain clean mother liquor, wherein the clean mother liquor serves as copper sulfate mother liquor to be used in the step 3 of the next preparation operation.
And 6, injecting a saturated copper sulfate solution into the second centrifugal machine, uniformly stirring, centrifuging for the fourth time, and carrying out solid-liquid separation to obtain the electroplating-grade wet copper sulfate pentahydrate. The mass ratio of the injected saturated copper sulfate solution to the copper sulfate pentahydrate crystal is as follows: 5:1, the concentration of copper ions in the saturated copper sulfate solution is 75g/L, the pH value is 2.5, the concentration of calcium ions is 50ppm, and the content of chloride ions is 10 ppm. And discharging the upper layer third solution into a saturated copper sulfate solution tank for storage, wherein when the content of calcium ions in the saturated copper sulfate solution in the tank is less than 200ppm and the concentration of chloride ions is less than 800ppm, the saturated copper sulfate solution can be recycled.
And 7, drying the electroplating-grade copper sulfate pentahydrate wet product at 40 ℃ to obtain electroplating-grade copper sulfate pentahydrate, and analyzing the impurity content of the prepared electroplating-grade copper sulfate pentahydrate, wherein the sum of the metal impurities except calcium in the electroplating-grade copper sulfate pentahydrate is less than 5ppm, the sum of the metal impurity contents is less than 5ppm, and the chlorine impurity content is less than 20 ppm. The content of metal impurities is analyzed by an ICP-OES method, the detection limit is 0.0003%, the content of chloride ions is analyzed by a UV-Vis method, the detection limit is 0.0010%, and the specific detection results are shown in the following table:
example 5
Referring to fig. 1 to 4, the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate comprises the following steps:
and 2, dissolving excessive copper acetate in pure water to prepare a copper ion saturated solution, dropwise adding acetic acid into the copper ion saturated solution, and adjusting the pH value to 3.0 to prepare an acid solution saturated with copper ions. 2.5kg of copper ion saturated acid solution is injected into a centrifuge, after continuous stirring is carried out for 30min at the rotating speed of 100rpm, secondary centrifugation is carried out, the rotating speed is 1000rpm, the centrifugation time is 10min, solid-liquid separation is carried out, then the second solution on the upper layer is discharged and discharged, the refining of crude basic copper carbonate is finished, refined basic copper carbonate is obtained, and the copper content in the refined basic copper carbonate is 51%;
and 3, injecting 35L of copper sulfate mother liquor into the reaction kettle, wherein the concentration of copper ions in the copper sulfate mother liquor is 75g/L, the pH value is 1.50, the calcium content is 336ppm, the chlorine content is 742ppm, adding 5kg of refined basic copper carbonate into the reaction kettle while stirring, after uniformly mixing, adjusting the temperature in the reaction kettle to ensure that the temperature in the reaction kettle is 30 ℃, slowly adding 3.25L of concentrated sulfuric acid, controlling the adding rate of the concentrated sulfuric acid to be 200ml/min, and discharging a large amount of bubbles in a reaction system in the mixing process. After the addition of concentrated sulfuric acid is finished, obtaining a first mother liquor, wherein the first mother liquor is supersaturated copper sulfate mother liquor, is in a dark blue transparent state, and has the temperature of 57.5 ℃ and the concentration of copper ions of 140 g/L;
and 5, transferring the first mixture into a settling tank 1, settling for 30min, precipitating the copper sulfate pentahydrate crystals to the bottom of the settling tank 1, starting a circulating pump to pump the mixed solution with higher content of the copper sulfate pentahydrate crystals at the bottom of the settling tank 1 to a second centrifugal machine through a first suction port 11, performing third centrifugation, performing solid-liquid separation, and discharging the upper-layer copper sulfate solution to obtain the copper sulfate pentahydrate crystals. The acid-proof pump is provided with a second suction inlet 12, and the distance between the second suction inlet 12 and the bottom of the tank body of the settling tank 1 is 25 percent of the height of the tank body.
The copper sulfate solution at the upper part in the settling tank 1 is a second mother solution, and after the copper sulfate pentahydrate crystals in the settling tank are lower than the height of the second suction inlet 12, the acid-resistant pump is started to pump the second mother solution, namely the copper sulfate solution at the upper layer out to the temporary storage tank 2 for temporary storage.
Through calcium concentration analysis sampling unit 5, carry out sample analysis and detection to the calcium ion concentration of second mother liquor in scratch pad groove 2, the calcium ion concentration is 557ppm in the second mother liquor in survey scratch pad groove 2, is greater than calcium saturated concentration 500ppm, carries out the decalcification to the second mother liquor in scratch pad groove 2.
Adding potassium fluoride and potassium hydroxide into water to prepare a calcium remover, replacing one third volume of second mother liquor in a temporary storage tank 2 by clean mother liquor, transferring the replaced second mother liquor serving as the mother liquor to be subjected to calcium removal into a calcium removal tank 3, adjusting the pH value of the calcium removal mother liquor in the calcium removal tank 3 to be 3.5 by using potassium hydroxide, adding the calcium remover in a stirring state, continuously stirring for 30min, standing for 3 hours to obtain the mother liquor subjected to calcium removal, filtering the mother liquor subjected to calcium removal by a microfiltration device, namely a calcium precipitate microfiltration unit 4 to obtain clean mother liquor, and using the clean mother liquor as copper sulfate mother liquor in the step 3 of the next preparation operation;
and 6, injecting a saturated copper sulfate solution into the second centrifugal machine, uniformly stirring, centrifuging for the fourth time, and carrying out solid-liquid separation to obtain the electroplating-grade wet copper sulfate pentahydrate. The mass ratio of the injected saturated copper sulfate solution to the copper sulfate pentahydrate crystal is as follows: 2.25:1, the concentration of copper ions in the saturated copper sulfate solution is 75g/L, the pH value is 2.0, the concentration of calcium ions is 50ppm, and the content of chloride ions is 10 ppm. And (3) discharging the upper layer third solution into a saturated copper sulfate solution tank for storage, wherein when the content of calcium ions in the saturated copper sulfate solution in the tank is more than 200ppm or the concentration of chloride ions is more than 800ppm, the saturated copper sulfate solution cannot be recycled, and the saturated copper sulfate solution with the calcium ions or the chloride ions exceeding the standard is used as the copper sulfate mother liquor in the step (3).
And 7, drying the electroplating-grade copper sulfate pentahydrate wet product at 40 ℃ to obtain electroplating-grade copper sulfate pentahydrate, and analyzing the impurity content of the prepared electroplating-grade copper sulfate pentahydrate, wherein the sum of the metal impurities except calcium in the electroplating-grade copper sulfate pentahydrate is less than 5ppm, the sum of the metal impurity contents is less than 5ppm, and the chlorine impurity content is less than 20 ppm. The content of metal impurities is analyzed by an ICP-OES method, the detection limit is 0.0003%, the content of chloride ions is analyzed by a UV-Vis method, the detection limit is 0.0010%, and the specific detection results are shown in the following table:
example 6
Referring to fig. 1 to 4, the method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate comprises the following steps:
and 2, dissolving excessive copper propionate in pure water to prepare a copper ion saturated solution, dropwise adding propionic acid into the copper ion saturated solution, and adjusting the pH value to 3.0 to prepare an acid solution saturated with copper ions. 2.5kg of copper ion saturated acid solution is injected into a centrifuge, after continuous stirring is carried out for 30min at the rotating speed of 100rpm, secondary centrifugation is carried out, the rotating speed is 1000rpm, the centrifugation time is 10min, solid-liquid separation is carried out, then the second solution on the upper layer is discharged and discharged, the refining of crude basic copper carbonate is finished, refined basic copper carbonate is obtained, and the copper content in the refined basic copper carbonate is 51%;
and 3, injecting 35L of copper sulfate mother liquor into the reaction kettle, wherein the concentration of copper ions in the copper sulfate mother liquor is 75g/L, the pH value is 1.50, the calcium content is 336ppm, the chlorine content is 742ppm, adding 5kg of refined basic copper carbonate into the reaction kettle while stirring, after uniformly mixing, adjusting the temperature in the reaction kettle to ensure that the temperature in the reaction kettle is 30 ℃, slowly adding 3.25L of concentrated sulfuric acid, controlling the adding rate of the concentrated sulfuric acid to be 200ml/min, and discharging a large amount of bubbles in a reaction system in the mixing process. After the addition of concentrated sulfuric acid is finished, obtaining a first mother liquor, wherein the first mother liquor is supersaturated copper sulfate mother liquor, is in a dark blue transparent state, and has the temperature of 57.5 ℃ and the concentration of copper ions of 130 g/L;
and 5, transferring the first mixture into a settling tank 1, settling for 30min, precipitating the copper sulfate pentahydrate crystals to the bottom of the settling tank 1, starting a circulating pump to pump the mixed solution with higher content of the copper sulfate pentahydrate crystals at the bottom of the settling tank 1 to a second centrifugal machine through a first suction port 11, performing third centrifugation, performing solid-liquid separation, and discharging the upper-layer copper sulfate solution to obtain the copper sulfate pentahydrate crystals. The acid-proof pump is provided with a second suction inlet 12, and the distance between the second suction inlet 12 and the bottom of the tank body of the settling tank 1 is 25 percent of the height of the tank body.
The copper sulfate solution at the upper part in the settling tank 1 is a second mother solution, and after the copper sulfate pentahydrate crystals in the settling tank are lower than the height of the second suction inlet 12, the acid-resistant pump is started to pump the second mother solution, namely the copper sulfate solution at the upper layer out to the temporary storage tank 2 for temporary storage.
Through calcium concentration analysis sampling unit 5, carry out sample analysis and detection to the calcium ion concentration in the second mother liquor in the groove 2 of keeping in, the calcium ion concentration is 588ppm in the second mother liquor in the groove 2 of survey and keeps in, is greater than calcium saturated concentration, carries out the calcium removal to the second mother liquor in the groove 2 of keeping in.
Adding sodium fluoride and sodium bicarbonate into water to prepare a calcium remover, replacing half volume of second mother liquor in the temporary storage tank 2 with pure water, transferring the replaced second mother liquor serving as the mother liquor to be subjected to calcium removal into a calcium removal tank 3, adjusting the pH value of the calcium removal mother liquor in the calcium removal tank 3 to be 3.5 with potassium hydroxide, adding the calcium remover in a stirring state, continuously stirring for 30min, standing for 3 hours to obtain the mother liquor subjected to calcium removal, filtering the mother liquor subjected to calcium removal by a microfiltration device, namely a calcium precipitate microfiltration unit 4 to obtain clean mother liquor, and using the clean mother liquor as copper sulfate mother liquor in the step 3 of the next preparation operation.
And 6, injecting a saturated copper sulfate solution into the second centrifugal machine, uniformly stirring, centrifuging for the fourth time, and carrying out solid-liquid separation to obtain the electroplating-grade wet copper sulfate pentahydrate. The mass ratio of the injected saturated copper sulfate solution to the copper sulfate pentahydrate crystal is as follows: 2.25:1, the concentration of copper ions in the saturated copper sulfate solution is 75g/L, the pH value is 2.0, the concentration of calcium ions is 50ppm, and the content of chloride ions is 10 ppm. And (3) discharging the upper layer third solution into a saturated copper sulfate solution tank for storage, wherein when the content of calcium ions in the saturated copper sulfate solution in the tank is more than 200ppm or the concentration of chloride ions is more than 800ppm, the saturated copper sulfate solution cannot be recycled, and the saturated copper sulfate solution with the calcium ions or the chloride ions exceeding the standard is used as the copper sulfate mother liquor in the step 3 of the next preparation operation.
And 7, drying the electroplating-grade copper sulfate pentahydrate wet product at 40 ℃ to obtain electroplating-grade copper sulfate pentahydrate, and analyzing the impurity content of the prepared electroplating-grade copper sulfate pentahydrate, wherein the sum of the metal impurities except calcium in the electroplating-grade copper sulfate pentahydrate is less than 5ppm, the sum of the metal impurity contents is less than 5ppm, and the chlorine impurity content is less than 20 ppm. The content of metal impurities is analyzed by an ICP-OES method, the detection limit is 0.0003%, the content of chloride ions is analyzed by a UV-Vis method, the detection limit is 0.0010%, and the specific detection results are shown in the following table:
the above description is only for the embodiments of the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. A method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate is characterized by comprising the following steps:
step 1, taking a certain amount of crude basic copper carbonate, adding a certain amount of pure water into the crude basic copper carbonate, stirring to obtain a first mixture, transferring the first mixture into a centrifugal machine, carrying out first centrifugation and solid-liquid separation, and then discharging an upper layer of first solution to obtain a first water washing substance;
step 2, injecting an acid solution saturated with copper ions into the centrifuge, stirring, carrying out secondary centrifugation, carrying out solid-liquid separation, and then discharging an upper layer of second solution to obtain refined basic copper carbonate;
step 3, injecting pure water or copper sulfate mother liquor into a reaction kettle, adding the refined basic copper carbonate into the reaction kettle while stirring, after uniformly mixing, adjusting the temperature in the reaction kettle, slowly adding concentrated sulfuric acid, and obtaining first mother liquor after the reaction is finished;
step 4, transferring the first mother liquor into a crystallization tank, cooling under the condition of continuous stirring, and separating out copper sulfate pentahydrate crystals from the first mother liquor to obtain a first mixture;
step 5, transferring the first mixture into a settling tank, after settling for a period of time, precipitating the copper sulfate pentahydrate crystals to the bottom of the settling tank, transferring the bottom copper sulfate pentahydrate crystals and part of the second mother liquor into a second centrifuge, performing third centrifugation, performing solid-liquid separation, discharging the upper layer of the second mother liquor to obtain the copper sulfate pentahydrate crystals, wherein the solution on the upper part of the settling tank is the second mother liquor, and pumping the second mother liquor into a temporary storage tank for storage;
step 6, injecting a saturated copper sulfate solution into the second centrifugal machine, uniformly stirring, performing fourth centrifugation, performing solid-liquid separation, and discharging an upper third solution to obtain an electroplating-grade wet copper sulfate pentahydrate product;
and 7, drying the electroplating-grade copper sulfate pentahydrate wet product to obtain the electroplating-grade copper sulfate pentahydrate.
2. The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate according to claim 1, wherein in the step 5, the second mother liquor is extracted into a temporary storage tank for storage, the calcium ion concentration of the second mother liquor in the temporary storage tank is sampled and analyzed, and when the calcium ion concentration is higher than the calcium saturation concentration, the second mother liquor is calcium saturated mother liquor, and calcium removal treatment is performed on the second mother liquor; when the calcium ion concentration is less than the calcium saturation concentration, the second mother liquor is used as copper sulfate mother liquor in the step 3, and the calcium saturation concentration is 500 ppm.
3. The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate as claimed in claim 2, wherein the calcium removal treatment comprises replacing a part of the second mother liquor with pure water or clean mother liquor, transferring the replaced part of the second mother liquor as the mother liquor to be calcium removed to a calcium removal tank, adjusting the pH value of the mother liquor to be calcium removed with an alkaline liquid, adding a calcium removal agent under stirring, continuing stirring for 30min, standing to obtain a mother liquor after calcium removal, and filtering the mother liquor after calcium removal by a microfiltration device to obtain clean mother liquor, wherein the clean mother liquor is used as the copper sulfate mother liquor in the step 3.
4. The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate according to claim 1, wherein the mass ratio of pure water to crude basic copper carbonate in the step 1 is 0.5:1-5: 1.
5. The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate according to claim 1, wherein the mass ratio of the copper ion saturated acidic solution to the crude basic copper carbonate in the step 2 is 1: 2.
6. The method of claim 1The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate is characterized in that the pH value of the acidic solution saturated with copper ions is 0.1-4.0, and the ion composition of the acidic solution saturated with copper ions is Cu2+And M2-The copper ion saturated acidic solution is prepared by dissolving soluble copper salt CuM in pure water and dissolving in acidic solution H2M is used for adjusting the pH value to obtain the compound.
7. The method of claim 6, wherein the saturated copper sulfate solution contains less than 200ppm calcium ions and less than 800ppm chloride ions.
8. The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate according to claim 1, wherein the mass ratio of the refined basic copper carbonate to the concentrated sulfuric acid in the step 3 is as follows: 2:1-2:1.3, wherein the temperature of the first mother liquor in the step 3 is 55-85 ℃, and the concentration of copper ions in the first mother liquor in the step 3 is 140 g/L.
9. The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate as claimed in claim 1, wherein the mass ratio of the saturated copper sulfate solution injected in the step 6 to the copper sulfate pentahydrate crystal is as follows: 0.5:1-5:1, the concentration of copper ions in the saturated copper sulfate solution is 70-80g/L, and the pH value of the saturated copper sulfate solution is 0.1-3.0.
10. The method for preparing electroplating-grade copper sulfate pentahydrate from crude basic copper carbonate as claimed in claim 1, wherein the settling tank comprises a tank body, a circulating pump and an acid-proof pump, the circulating pump is provided with a first suction inlet, the first suction inlet is positioned at the bottom of the tank body, the acid-proof pump is provided with a second suction inlet, and the distance between the second suction inlet and the bottom of the tank body is 15% -50% of the height of the tank body.
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