Hollow spherical copper hydroxide and preparation method therefor

Abstract

Hollow spherical copper hydroxide and a preparation method therefor. The preparation method comprises: uniformly mixing a seed crystal with water to obtain a seed crystal dispersion, wherein the seed crystal comprises hydrochloric-acid-catalyzed basic copper chloride; adding an impurity-removed acidic copper-containing etching waste liquid, ammonia water and a stabilizer to the seed crystal dispersion to obtain a mixed reactant with a pH value of 4-5.5; and heating the mixed reactant at a heating temperature of 40-80°C, stirring same at a stirring speed of 100-200 r / min, separating out a solid substance after reaction, then drying same to obtain an intermediate, wherein the intermediate comprises spherical basic copper chloride; uniformly mixing the intermediate and a solvent to obtain an intermediate dispersion; adding ammonia water to the intermediate dispersion while stirring, wherein the mass ratio of the intermediate to the ammonia water is (1 : 1.05)-(1 : 1.15), separating out a precipitate after reaction, then washing and drying same to obtain the hollow spherical copper hydroxide.

Description

Hollow spherical copper hydroxide and preparation method thereof Technical Field

[0001] The present application relates to the technical field of copper hydroxide preparation, and in particular to a hollow spherical copper hydroxide and a preparation method thereof. Background Art

[0002] Copper hydroxide, with the molecular formula Cu(OH)2, appears as blue granules. It is insoluble in water, slightly amphoteric, and soluble in acid and ammonia. Its color darkens upon heating, and it decomposes into black copper oxide and water at high temperatures. It is commonly used as an analytical reagent and in the pharmaceutical field. It can also be used as a raw material to prepare copper hydroxide preparations for use in pesticides and fungicides.

[0003] The conventional method for preparing copper hydroxide is to react a solution containing copper ions (such as a copper chloride solution or a copper sulfate solution) with an alkaline substance such as sodium hydroxide or potassium hydroxide to precipitate and collect the precipitate. Because copper hydroxide is a heat-sensitive compound, the acid-base neutralization precipitation reaction involving strong alkaline substances such as sodium hydroxide and potassium hydroxide is highly exothermic and violent. As a result, the copper hydroxide prepared by conventional industrial methods is often amorphous or even muddy in shape, dark or even black in color, and of low purity, making large-scale production difficult. This reduces the application value of copper hydroxide.

[0004] Summary of the Invention

[0005] In view of this, the present application provides a hollow spherical copper hydroxide and a preparation method thereof.

[0006] To achieve the above-mentioned objectives, the present application provides a method for preparing hollow spherical copper hydroxide, the preparation method comprising: uniformly mixing seed crystals and water to obtain a seed crystal dispersion, wherein the seed crystals include hydrochloric acid-catalyzed basic copper chloride; adding impurity-removed acidic copper-containing etching waste liquid, ammonia water and a stabilizer to the seed crystal dispersion to obtain a mixed reactant with a pH value of 4 to 5.5; heating the mixed reactant at a heating temperature of 40 to 80° C. and stirring the mixed reactant at a stirring speed of 100 to 200 r / min, separating the solid matter after the reaction, and drying to obtain an intermediate, wherein the intermediate includes spherical basic copper chloride.

[0007] The intermediate and the solvent are uniformly mixed to obtain an intermediate dispersion; aqueous ammonia is added to the intermediate dispersion and stirred, wherein the mass ratio of the intermediate to the aqueous ammonia is 1:1.05 to 1:1.15; after the reaction, the sediment is separated, washed, and dried to obtain the hollow spherical copper hydroxide.

[0008] In some possible implementations, the reaction temperature of the intermediate dispersion and the ammonia water is 40-60°C.

[0009] In some possible implementations, the stirring speed of the reaction between the intermediate dispersion and the ammonia water is 50 to 100 r / min.

[0010] In some possible implementations, the mass ratio of the intermediate to the solvent is 1:1 to 2:1.

[0011] In some possible implementations, the mass fraction of the ammonia water is 15-30%.

[0012] In some possible implementations, the reaction time of the intermediate dispersion and the ammonia water is 0.5 h to 2 h.

[0013] In some possible implementations, the solvent is water or a base liquid, and the base liquid is a liquid recovered from washing the sediment.

[0014] In some possible implementations, the temperature for drying the sediment is 50-105°C.

[0015] The present application also provides a hollow spherical copper hydroxide, which is prepared according to the preparation method.

[0016] In some possible implementations, the hollow spherical copper hydroxide includes a hollow portion, and the hollow portion occupies 1 / 4.5 to 1 / 3.5 of the total volume of the hollow spherical copper hydroxide.

[0017] The present application is in the step of preparing spherical basic copper chloride intermediate, using hydrochloric acid to catalyze basic copper chloride as seed, copper and ammonia react in acidic copper-containing etching waste liquid, and the reaction product grows rapidly on the surface of the seed and forms crystals, and the crystals continue to grow to form spherical basic copper chloride. During the crystal crystallization growth process, the reaction temperature is controlled to control the growth rate of the seed, and the morphology of the crystal is controlled by controlling the stirring speed, so as to control the growth of the crystal, so that the surface of the crystal is irregularly grown to a regular sphere, and then spherical basic copper chloride is obtained, and the crystals on the surface of the crystal are ground during continuous stirring, which strengthens the structural strength of the crystal, so that the surface of the crystal finally obtained is not only smooth but also has good overall structural stability and high hardness. The spherical basic copper chloride prepared by the present application has a particle size of 50 to 100 μm and a purity of up to 99%. Then, an intermediate dispersion containing spherical basic copper chloride and ammonia water are mixed in a certain ratio to react. The copper and chlorine elements of some of the spherical basic copper chloride combine with the ammonia water to form a liquid phase diammine copper chloride [Cu(NH3)2Cl2] complex, which enters the solution, thereby converting the spherical basic copper chloride into hollow spherical copper hydroxide. The preparation method of the present application is simple and controllable, conducive to large-scale production, with a particle size of 5 to 200 μm, a purity of more than 98%, good stability, and storage for up to 1.5 years without discoloration or agglomeration. The prepared hollow spherical copper hydroxide has a large specific surface area, making the copper hydroxide widely applicable to dyeing, sterilization, or catalyst fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG1 is an X-ray diffraction pattern of the intermediate prepared in Example 1 of the present application.

[0019] FIG2 is an X-ray diffraction pattern of the hollow spherical copper hydroxide prepared in Example 1 of the present application.

[0020] FIG3 is a microscope image of the intermediate prepared in Example 1 of the present application at a magnification of 200 times.

[0021] FIG4 is a microscope image of the intermediate prepared in Comparative Example 1 of the present application at a magnification of 200 times.

[0022] FIG5 is a microscope image of the intermediate prepared in Comparative Example 2 of the present application at a magnification of 200 times.

[0023] FIG6 is a microscope image of the hollow spherical copper hydroxide prepared in Example 1 of the present application at a magnification of 200 times.

[0024] FIG7 is a microscope image of a cross section of the hollow spherical copper hydroxide prepared in Example 1 of the present application at a magnification of 200 times. DETAILED DESCRIPTION

[0025] The embodiments of the present invention are described in detail below. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be understood as limiting the present invention.

[0026] Throughout this specification, references to terms such as "one embodiment," "some embodiments," "examples," "specific examples," or "some examples" indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0027] Acidic copper-containing etching waste liquid is the etching waste liquid discharged after etching the printed circuit board (PCB), which contains a large amount of copper chloride, hydrochloric acid and a small amount of ammonium chloride.

[0028] The present application provides a method for preparing hollow spherical copper hydroxide, which comprises:

[0029] S1. Mixing seed crystals and water uniformly to obtain a seed crystal dispersion, wherein the seed crystals include hydrochloric acid-catalyzed basic copper chloride.

[0030] Specifically, this step may include adding water and seed crystals into a reactor and stirring to obtain the seed crystal dispersion, wherein the volume of the water is about 1 / 5 of the reactor, and the mixture is stirred sufficiently to uniformly disperse the seed crystals in the water.

[0031] Hydrochloric acid-catalyzed basic copper chloride is a product obtained by chemically catalyzing the weathering of crystalline basic copper chloride with hydrochloric acid, causing the crystal particles to expand and fragment. Hydrochloric acid-catalyzed basic copper chloride is insoluble in water. Seed crystals are added to water and stirred thoroughly to ensure uniform dispersion, facilitating subsequent reactions.

[0032] The preparation method of hydrochloric acid-catalyzed basic copper chloride is prior art, and for details, reference may be made to Patent No. 200810218161.2, which is not described in detail here. In this embodiment, the hydrochloric acid-catalyzed basic copper chloride is preferably prepared using the method of Example 1 in the aforementioned patent. The difference between this embodiment and Example 1 is that the acetic acid in Example 1 is replaced with hydrochloric acid, while other conditions remain unchanged to obtain the hydrochloric acid-catalyzed weathered basic copper chloride product.

[0033] The hydrochloric acid-catalyzed basic copper chloride has a rough surface, a surface depression, and relatively small crystal particles. There are various types of basic copper chloride crystals. The microscopic morphology and stability of basic copper chloride prepared from basic copper chlorides of different crystalline forms as seed crystals are different, and they can also be converted into each other under certain conditions. In this application, hydrochloric acid-catalyzed basic copper chloride is used as seed crystal, which is beneficial for subsequent crystals to form stable spherical basic copper chloride during the crystal growth process and enables subsequent crystals to grow into crystals of uniform size.

[0034] S2. Adding the impurity-removed acidic copper-containing etching waste liquid, ammonia water and a stabilizer to the seed crystal dispersion to obtain a mixed reactant with a pH value of 4 to 5.5.

[0035] In this process, since the acidic copper-containing etching waste liquid is highly acidic, the addition of ammonia water can adjust the pH of the reaction, and the reaction can be controlled and mild, which is beneficial for treating the wastewater used in the subsequent preparation of spherical basic copper chloride in this application. At the same time, ammonia water is also added as a reactant and is cheap and readily available. In some embodiments, the pH can be 4, 4.5, 5 or 5.5.

[0036] The acidic copper-containing etching waste liquid refers to the acidic etching waste liquid of printed circuit boards, which contains copper ions and chloride ions. In some embodiments, the impurity-removed acidic copper-containing etching waste liquid refers to the acidic copper-containing etching waste liquid obtained after removing impurities including but not limited to dioxins, arsenic, lead, cadmium, and insoluble solids.

[0037] Among them, the impurity removal step of the acidic copper-containing etching waste liquid is a prior art. For details, please refer to the records of Patent Nos. 200810141671.4 and 201010567599.9, which will not be repeated here.

[0038] S3. The mixed reactants are heated to a temperature of 40 to 80°C and stirred at a speed of 100 to 200 rpm. After the reaction, the solid matter is separated and dried to obtain an intermediate, which includes spherical basic copper chloride. The main chemical reaction in this step is: 2CuCl2 + 3NH3·H2O = Cu2(OH)3Cl + 3NH4Cl

[0039] Through the above reaction, Cu2(OH)3Cl grows on the surface of the basic copper chloride seed crystal catalyzed by hydrochloric acid and crystallizes to form spherical basic copper chloride.

[0040] Using hydrochloric acid to catalyze basic copper chloride as seed, copper and ammonia react in acidic copper-containing etching waste liquid, and reaction product grows quickly on seed surface and forms crystal, and crystal grows continuously and stabilizes the overall structure of crystal under the action of stabilizer, to obtain stable spherical basic copper chloride. In crystal crystallization growth process, control reaction temperature to control the growth rate of crystal, and by controlling stirring speed to control the morphology of crystal, thus control the growth of crystal, make the surface of its crystal by irregular growth to form a regular sphere, and then obtain spherical basic copper chloride, and in the continuous stirring process, the crystal body on the surface of crystal is ground, the structural strength of crystal body is reinforced, so that the surface of the crystal body finally obtained is not only smooth and the overall structural stability of crystal body is good, and hardness is high. The spherical basic copper chloride particle size prepared by the present application is between 50~100 μm, and purity can reach 99%, can be used as the production raw material of downstream copper salt products (such as copper hydroxide or copper chloride, etc.), can also be used as the raw material of inorganic copper preparation (such as copper oxychloride) in adding feed additive copper source and pesticide. At the same time, the spherical basic copper chloride prepared in the present application has a stable structure, good storage resistance, good dispersibility and good structural uniformity.

[0041] In the above-mentioned preparation process, reaction temperature and stirring speed affect the formation of spherical basic copper chloride crystals, reaction product Cu2(OH)3Cl is in the growth of seed crystal surface crystallization, and this process is the process of being worn to regular spherical surface by the irregular surface of crystal surface.Under the above-mentioned suitable reaction temperature condition, be conducive to the growth of crystal and form spherical basic copper chloride, and control stirring speed in the growth process of crystal, control the wear rate on crystal surface, thereby make the growth rate of crystal and the wear rate on crystal surface reach balance, and then obtain the spherical basic copper chloride of smooth surface.In actual production process, if the growth rate of crystal is less than wear rate, then owing to the inadequate degree of wear on crystal surface, the morphology of the crystal obtained is irregular, and its overall structural stability is not good enough.Therefore, in the growth process of crystal, need to control the growth rate of crystal and can not be greater than wear rate.

[0042] In this embodiment, the reaction temperature is 40-80°C. If the reaction temperature is too high, such as above 80°C, the crystal aging after growth is accelerated, the crystal hardness increases, and the wear rate of the crystal surface is relatively reduced. If the reaction temperature is too low, such as below 40°C, the growth rate of the crystal is affected, making it difficult for the crystal to form a spherical shape. In some embodiments, the reaction temperature can be 40°C, 45°C, 50°C, 55°C, 60°C, 70°C, or 80°C.

[0043] In this embodiment, the stirring speed is 100 to 200 r / min. If the stirring speed is low, such as less than 100 r / min, the stirring speed is insufficient, the probability of contact wear between the crystals decreases, and the wear rate of the crystals is reduced to a certain extent, and basic copper chloride with other morphologies will eventually be formed. If the stirring speed is fast, the wear on the crystal surface is large, and it is difficult to deposit spherical basic copper chloride of a certain particle size on the crystal surface. In some embodiments, the stirring speed is 100 r / min, 120 r / min, 140 r / min, 150 r / min, 160 r / min, 180 r / min or 200 r / min.

[0044] In some embodiments, the flow ratio of the acidic copper-containing etching waste liquid to the ammonia water is 2:1 to 6:1, the concentration of copper ions in the acidic copper-containing etching waste liquid is 80 to 150 g / L, and the mass fraction of the ammonia water is 15 to 30%. Under the above-mentioned suitable flow ratio, concentration, and mass fraction conditions, the copper in the acidic copper-containing etching waste liquid and the ammonia water can be promoted to fully react, and the addition of too much ammonia water can be avoided. In some embodiments, the flow ratio of the acidic copper-containing etching waste liquid to the ammonia water is 2:1, 3:1, 4:1, 5:1, or 6:1. The concentration of copper ions is 80 g / L, 90 g / L, 100 g / L, 110 g / L, 120 g / L, or 150 g / L. The mass fraction of the ammonia water is 15%, 20%, 25%, or 30%.

[0045] In some embodiments, the content of the seed crystals in the mixed reactants is 50-150 kg / m 3 According to the addition amount of the above acidic copper-containing etching waste liquid and ammonia water, within such a range, the reaction product grows on the seed crystal. In some embodiments, the content of the seed crystal is 50kg / m 3 、60kg / m 3 、80kg / m 3 , 100kg / m 3 , 120kg / m 3 、130kg / m 3 or 150kg / m 3 In some embodiments, the seed crystals have a particle size of 0.1 μm to 50 μm.

[0046] In some embodiments, the flow rate of the acidic copper-containing etching waste liquid is 2 to 3 m 3 / h, within this flow rate range, and by correspondingly controlling the flow rate of ammonia water, the acidic copper-containing etching waste liquid and ammonia water are fully reacted. At the same time, it is also beneficial to combine the reaction conditions such as temperature and stirring rate in the entire preparation reaction process to control the morphology of the reaction product and avoid excessive flow rate and uncontrollable product growth. In some embodiments, the flow rate is 2m 3 / h、2.5m3 / h、2.8m 3 / h or 2m 3 / h.

[0047] In some embodiments, the reaction time is 2 to 8 hours to maintain a certain growth rate of the crystals in the reactor. The reaction time is inversely proportional to the concentration of the acidic basic copper chloride waste liquid and the ammonia water. Different from the layered growth mode of other morphological basic copper chlorides, the crystal growth mode of spherical basic copper chloride belongs to the diamond-like sphere structure growth mode, which has extremely high requirements for the growth rate of the crystal. When the growth rate is too fast, the deposition rate on the crystal surface is too fast, and the growth mode will become a layered growth mode, which is easy to form other crystal forms of basic copper chloride, causing the crystal surface to grow into irregular morphologies such as jagged shapes. Therefore, it is necessary to control the growth rate of the crystal by controlling the flow rate of the acidic basic copper chloride waste liquid, the flow rate of the ammonia water and the reaction time.

[0048] In some embodiments, during the reaction process, the growth rate of spherical basic copper chloride is less than 2 μm / h, and the growth rate of the crystal is controlled to be no more than 2 μm / h, specifically 1.8 μm / h, 1.5 μm / h, 1.3 μm / h, 1 μm / h or 0.5 μm / h. 1 μm / h is preferred. In the above process, the growth rate is controlled to be 2 μm / h, and the particle size of the seed crystal is used as the initial particle size. The particle size of the spherical basic copper chloride to be achieved is the target particle size. The particle size difference between the target particle size and the initial particle size is used to calculate the growth rate of the crystal per hour, thereby calculating the growth rate.

[0049] In some embodiments, the stabilizer is ammonium bicarbonate, and the amount of the stabilizer added is 1 / 1000 to 1 / 100 of the total mass of the seed dispersion, the acidic copper-containing etching waste liquid and the ammoniacal liquor. During the preparation process, the stabilizer and water are mixed to form a solution with a mass fraction of 30% and added in proportion. The addition of the stabilizer can stabilize the crystal form of the spherical basic copper chloride, and finally obtain a stable spherical basic copper chloride. In some embodiments, the amount of the stabilizer added can be 1 / 1000, 1 / 800, 1 / 500, 1 / 300 or 1 / 100 of the total mass of the reactants (seed dispersion, acidic copper-containing etching waste liquid and ammoniacal liquor).

[0050] The specific separation method in step S3 is as follows: the product after the reaction of the mixed reactants is transported to a cyclone for separation, the separated solid matter is collected, and dried to obtain a spherical basic copper chloride intermediate.

[0051] In some embodiments, a cyclone is used for hydrocyclone separation, and the rotation speed of the cyclone is 30 to 70 r / min. Solid matter and suspended material are separated, and the suspended material is recovered and added to the reactor again as a mixed reactant to react, thereby improving the utilization rate of the mixed reactant and saving costs. The cyclone separation technology can be used to screen out basic copper chloride that meets the particle size and morphology requirements in the reaction product. Some basic copper chloride with smaller particle size is mixed in the suspended material. The suspended material is added to the mixed reactant again and allowed to continue reacting to collect more spherical basic copper chloride. In some embodiments, the rotation speed of the cyclone can be 30 r / min, 40 r / min, 50 r / min or 70 r / min.

[0052] In some embodiments, the temperature for drying the solid material is 50 to 130° C. to fully dry the solid material, reduce the water content in the solid material, improve the structural stability of the final product, spherical basic copper chloride, and avoid agglomeration due to the presence of water in the basic copper chloride during subsequent storage. In actual production, the wet solid material separated from the cyclone can be fully dried within the above temperature range. The above drying temperature can be 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C. or 130° C.

[0053] The spherical basic copper chloride prepared in this application has a smooth surface, a particle size of 50 to 100 μm, and a purity of more than 99%. The spherical basic copper chloride prepared in this application can be used as a raw material for the production of downstream copper salt products such as copper hydroxide and copper chloride, can also be used as a copper source for feed additives, and can also be used as a raw material for the inorganic copper preparation copper oxychloride in the pesticide field. Furthermore, because the basic copper chloride prepared by this method has a special spherical morphology, it has greater application and development value in fields such as materials science.

[0054] S4. The intermediate prepared in step S3 and the solvent are mixed uniformly to obtain an intermediate dispersion.

[0055] Since spherical basic copper chloride is insoluble in water, the intermediate and the solvent are mixed evenly so that the intermediate can be evenly dispersed in the solvent, which is beneficial to subsequent reactions.

[0056] In some implementations, the solvent is water or a bottom liquid, and the bottom liquid is a liquid recovered from washing the sediment.

[0057] S5. Adding ammonia water to the intermediate dispersion and stirring, wherein the mass ratio of the intermediate to the ammonia water is 1:1.05 to 1:1.15, separating the sediment after the reaction, washing, and drying to obtain the hollow spherical copper hydroxide.

[0058] In the step of preparing hollow spherical copper hydroxide, an intermediate dispersion containing spherical basic copper chloride and ammonia water are mixed in a certain proportion to react. The ammonia water reacts with the spherical basic copper chloride, and the copper and chlorine elements of part of the spherical basic copper chloride combine with the ammonia water to form a liquid phase diammine copper chloride [Cu(NH3)2Cl2] complex and enter the solution, thereby converting the spherical basic copper chloride into hollow spherical copper hydroxide. The preparation method of the present application is simple and controllable, which is conducive to large-scale production. The particle size is 5 to 200 μm, the purity is above 98%, the stability is good, and it can be stored for up to 1.5 years without discoloration or caking. The prepared hollow spherical copper hydroxide has a large specific surface area, so that the copper hydroxide can be widely used in dyeing, sterilization or catalyst fields.

[0059] The main chemical reaction in this step is: 2Cu2(OH)3Cl+2NH3·H2O=3Cu(OH)2+Cu(NH3)2Cl2+2H2O

[0060] Under the above reaction conditions, ammonia reacts with spherical basic copper chloride, and ammonia reacts with part of the copper and chlorine, consuming 1 / 4 of the copper and all of the chlorine in the spherical basic copper chloride itself and forming a liquid phase diammine copper chloride [Cu(NH3)2Cl2] complex product and flowing into the solution. After the reaction, the spherical basic copper chloride is converted into copper hydroxide. In the above reaction, since the solution environment on the surface of the spherical basic copper chloride is consistent and the solution is first contacted, the above reaction occurs preferentially on the surface of the spherical basic copper chloride. With the passage of reaction time and the deepening of the reaction, the solution gradually immerses into the middle part of the spherical basic copper chloride and continues to react inside the sphere, while continuously releasing the diammine copper chloride complex product into the solution. During the reaction, there is an interconnected interface inside the spherical basic copper chloride crystal particles, and the reaction also gradually penetrates into the middle part of the spherical basic copper chloride along the interface. When the reaction reaches the center of the spherical basic copper chloride, the center is the basic copper chloride initially formed, which is relatively unstable, and the center of the sphere is most obviously subjected to stress concentration, resulting in the copper hydroxide formed by the reaction in the center being unstable and moving radially toward the surface of the sphere, making the center of the sphere hollow, and ultimately forming a hollow spherical copper hydroxide.

[0061] The mass ratio of the intermediate to the ammonia water is 1:1.05 to 1:1.15. Within this ratio range, the ammonia water and the intermediate can fully react. If this ratio is too small, the ammonia water will be excessive, resulting in a waste of raw materials, and it will also avoid the reaction of excess ammonia water and copper hydroxide to form ammonia copper chloride complex; if this ratio is too large, the ammonia water will be insufficient, and the spherical basic copper chloride and ammonia water will not react completely, resulting in a mixture of spherical basic copper chloride and hollow spherical copper hydroxide. In some embodiments, the mass ratio of the two is 1:1.05, 1:1.1 or 1:1.05.

[0062] In some embodiments, the reaction temperature of the intermediate dispersion and aqueous ammonia is 40-60°C. This temperature can accelerate the reaction rate. If the reaction temperature is below 40°C, the reaction rate is not significantly accelerated. If the reaction temperature is above 60°C, the copper hydroxide obtained may undergo dehydration to form copper oxide, resulting in an impure product with a dark color. In some embodiments, the reaction temperature is 40°C, 45°C, 50°C, 55°C, or 60°C.

[0063] In some embodiments, the stirring speed of the reaction between the intermediate dispersion and the ammonia solution is 50 to 100 r / min to ensure that the intermediate dispersion and the ammonia solution are fully mixed and promote uniform reaction. In some embodiments, the stirring speed is 50 r / min, 60 r / min, 70 r / min, 80 r / min, 90 r / min, or 100 r / min.

[0064] In some embodiments, the mass ratio of the intermediate to the solvent is 1:1 to 2:1, so that the intermediate can be evenly dispersed in the solvent. The mass ratio of the intermediate to the solvent is 1:1, 1.5:1 or 2:1.

[0065] In some embodiments, the mass fraction of ammonia water is 15-30%, and the flow rate of ammonia water added to the intermediate dispersion is 0.5-1.5 m 3 / h. Controlling the flow rate of ammonia water can control the reaction between ammonia water and spherical basic copper chloride, avoiding excessive ammonia water flow rate, which will cause a large amount of ammonia water to contact the intermediate, so that the copper hydroxide after the reaction forms an ammonia-copper chloride complex. The mass fraction of ammonia water can be 15%, 20%, 25% or 30%; the flow rate of ammonia water is 0.5m 3 / h、1.0m 3 / h or 1.5m 3 In some embodiments, the flow rate of the ammonia solution can be calculated according to the formula v=V / t, where v is the flow rate of the ammonia solution, V is the effective volume of the reaction container, and t is the reaction time of the intermediate dispersion and the ammonia solution.

[0066] In some embodiments, the reaction time of the intermediate dispersion and aqueous ammonia is 0.5 h to 2 h to fully react and obtain copper hydroxide. The reaction time can be 0.5 h, 1 h, 1.5 h or 2 h.

[0067] In some embodiments, the temperature for drying the sediment is 50°C to 105°C. Within this range, while ensuring a certain drying efficiency, excessively high temperatures are avoided, which may cause the copper hydroxide to dehydrate and convert into copper oxide, resulting in an impure product with a black color. The drying temperature may be 50°C, 60°C, 80°C, 100°C, or 105°C.

[0068] The present application also provides a hollow spherical copper hydroxide prepared by the above-described preparation method. The hollow spherical copper hydroxide prepared by the present application is blue in color, has a particle size of 5 to 200 μm, and a purity of over 98%. It can be stably stored at room temperature for over 1.5 years without discoloration or agglomeration, and has excellent stability.

[0069] In some embodiments, the hollow spherical copper hydroxide includes a hollow portion, which accounts for 1 / 4.5 to 1 / 3.5 of the total volume of the hollow spherical copper hydroxide. Compared with copper hydroxides of other morphologies, the formation of the hollow portion increases the specific surface area of ​​the spherical copper hydroxide, and to a certain extent also improves the activity and bactericidal property of copper hydroxide as a bactericide.

[0070] The hollow spherical copper hydroxide prepared in this application can be used as a raw material for the production of downstream copper salt products such as copper oxide, copper carbonate, copper chloride, and copper sulfate. It can also be used as a raw material for copper hydroxide preparations, a pesticide fungicide. Furthermore, due to the unique hollow spherical morphology of the copper hydroxide prepared by this method, it has a larger specific surface area than copper hydroxide prepared by other methods. This characteristic can make hollow spherical copper hydroxide more advantageous in applications such as materials or catalysts.

[0071] The present invention will be explained below with reference to the embodiments. Those skilled in the art will appreciate that the following examples are intended only to illustrate the present invention and are not to be construed as limiting the present invention. Unless otherwise indicated, the reagents, software, and instruments not specifically described in the following examples are all conventional commercially available products or open source.

[0072] The composition of the impurity-removed acidic copper-containing etching waste liquid of the present application is shown in Table 1. The following examples and comparative examples of the present application all use impurity-removed acidic copper-containing etching waste liquid, which refers to the acidic copper-containing etching waste liquid obtained after removing impurities such as dioxins, arsenic, lead, cadmium, nickel and insoluble solids.

[0073] Table 1 Component content in the acidic copper-containing etching waste liquid after impurity removal

[0074] Example 1

[0075] In a 5 cubic meter reactor, 1 cubic meter of water was added, and 0.5 kg of hydrochloric acid-catalyzed basic copper chloride seed crystals were added, and the mixture was stirred thoroughly to obtain a seed crystal dispersion.

[0076] 2m 3 The flow rate will be 2m / h 3 The above acidic copper etching waste liquid, with 0.5m 3 The flow rate will be 0.5m / h 3Ammonia water with a mass fraction of 20% and 5.8 kg of ammonium bicarbonate stabilizer were simultaneously added to the reactor at a rate of 5.8 kg / h and mixed with the seed crystal dispersion to obtain a mixed reactant with a pH of 4.8.

[0077] The mixed reactants were heated and stirred continuously at 180 rpm at 45°C for 5 hours. The reaction was then transferred to a cyclone for hydrocyclone separation at 50 rpm to separate the solids and suspended material. The suspended material was then added back to the reactor for re-reaction. The collected solids were dried at 70°C for 5 hours to obtain a spherical basic copper chloride intermediate.

[0078] 150 kg of spherical basic copper chloride and water were added to the reactor at a mass ratio of 1:1 and stirred evenly to obtain an intermediate dispersion. 20% ammonia water was added at a mass ratio of spherical basic copper chloride and ammonia water of 1:1.05 and stirred continuously. The flow rate of ammonia water was 1m 3 / h, the reaction temperature was 40°C, the stirring speed was 60r / min, and after reacting for 50 minutes, the precipitate was filtered to obtain a sediment. The sediment was washed with water several times and dried at 100°C to obtain 96kg of hollow spherical copper hydroxide with an average particle size of 50μm.

[0079] Comparative Example 1

[0080] The difference between Comparative Example 1 and Example 1 is that the seed crystals used in Comparative Example 1 are acetic acid-catalyzed weathering of basic copper chloride products (the specific preparation steps are described in Example 1 of Patent No. 200810218161.2), and a basic copper chloride intermediate is prepared.

[0081] Comparative Example 2

[0082] Comparative Example 2 differs from Example 1 in that no seed crystals or stabilizer were added to the reactor to prepare a basic copper chloride intermediate. Referring to Figures 1 and 2, the present application performed X-ray diffraction tests on the intermediate and hollow spherical copper hydroxide prepared in Example 1, respectively. The analytical instrument used was an X-ray diffractometer (SHIMADZU XRD-6000, D / max 2500v / pc, Cu Kα radiation), with a continuous scanning mode, a scanning range of 10-75deg and 5-90deg, a scanning speed of 5deg / min, a present time of 1.00sec, a voltage of 40kV, and a current of 30A.

[0083] As can be seen from Figure 1, the XRD pattern of the intermediate obtained in Example 1 has a good match with card 78-0372 (Cu2Cl(OH)3, Atacamite). The product belongs to the orthorhombic system Pnma(62) with unit cell parameters of 6.03×6.865×9.12 (90.0×90.0×90.0). This indicates that the intermediate prepared in Example 1 is a basic copper chloride product.

[0084] As shown in FIG2 , the XRD pattern of the hollow spherical copper hydroxide prepared in Example 1 has a good match with that of card 80-0656 (Cu(OH)2, Copper Hydroxide). The product belongs to the orthorhombic system Cmc21 (36), with unit cell parameters of 2.9471×10.593×5.2564 (90.0×90.0×90.0). This proves that copper hydroxide was prepared in Example 1.

[0085] The present application also conducted microscope tests at a magnification of 200 times on the intermediate, hollow spherical copper hydroxide, and the cross section of the hollow spherical copper hydroxide prepared in Example 1. The analysis instrument was a metallographic microscope (analytical instrument: German Leica DM2500M).

[0086] As can be seen from Figure 3, the intermediate crystals are (dark) green spherical, with smooth particle surfaces, uniform particles, and uniform dispersion. This indicates that Example 1 prepared spherical basic copper chloride.

[0087] At the same time, the present application also conducted a microscope test of magnification on the basic copper chloride products prepared in Comparative Examples 1 and 2. As can be seen from Figure 4, the surface of the basic copper chloride product has many sharp corners and edges, is irregular, and does not form spherical particles. This shows that in Example 1, hydrochloric acid is used to catalyze basic copper chloride as a seed crystal. During the preparation process, the chloride ions in the hydrochloric acid will act on the basic copper chloride, which is conducive to the subsequent formation of spherical basic copper chloride.

[0088] As can be seen from Figure 5, the surface of the basic copper chloride prepared without the addition of seed crystals and stabilizers also has many sharp corners and edges, and the particles are uneven in size and irregular in shape. This shows that the combination of seed crystals and stabilizers is conducive to the formation of spherical basic copper chloride.

[0089] As can be seen from Figure 6, the hollow spherical copper hydroxide crystals are blue spherical, with uniform and evenly dispersed crystal particles. As can be seen from Figure 7, the cross-section of a single particle is hollow spherical, with a particle diameter of approximately 61.5 μm, a spherical shell thickness of approximately 31 μm, and an internal hollow sphere diameter of approximately 30.6 μm. Combined with Figures 6 and 7, this demonstrates that Example 1 produced hollow spherical copper hydroxide.

[0090] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent replacements of the technical solutions of the present invention should not depart from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing hollow spherical copper hydroxide, characterized in that: The preparation method comprises: Mixing seed crystals and water uniformly to obtain a seed crystal dispersion, wherein the seed crystals include hydrochloric acid-catalyzed basic copper chloride; Adding the impurity-removed acidic copper-containing etching waste liquid, ammonia water and a stabilizer to the seed crystal dispersion to obtain a mixed reactant with a pH value of 4 to 5.5; The mixed reactants are heated at a temperature of 40 to 80° C. and stirred at a stirring speed of 100 to 200 r / min. After the reaction, solid matter is separated and dried to obtain an intermediate, wherein the intermediate includes spherical basic copper chloride; uniformly mixing the intermediate and the solvent to obtain an intermediate dispersion; Ammonia water is added to the intermediate dispersion and stirred, wherein the mass ratio of the intermediate to the ammonia water is 1:1.05 to 1:1.

15. After the reaction, the sediment is separated, washed, and dried to obtain the hollow spherical copper hydroxide.

2. The method for preparing hollow spherical copper hydroxide according to claim 1, wherein: The reaction temperature of the intermediate dispersion and the ammonia water is 40-60°C.

3. The method for preparing hollow spherical copper hydroxide according to claim 1, characterized in that: The stirring speed of the intermediate dispersion and the ammonia water is 50-100 r / min.

4. The method for preparing hollow spherical copper hydroxide according to claim 1, wherein: The mass ratio of the intermediate to the solvent is 1:1 to 2:

1.

5. The method for preparing hollow spherical copper hydroxide according to claim 1, wherein: The mass fraction of the ammonia water is 15-30%.

6. The method for preparing hollow spherical copper hydroxide according to claim 1, characterized in that: The reaction time of the intermediate dispersion and the ammonia water is 0.5 h to 2 h.

7. The method for preparing hollow spherical copper hydroxide according to claim 1, characterized in that: The solvent is water or a base liquid, and the base liquid is a liquid recovered by washing the sediment.

8. The method for preparing hollow spherical copper hydroxide according to claim 1, characterized in that: The temperature for drying the sediment is 50-105°C.

9. A hollow spherical copper hydroxide, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 8.

10. The hollow spherical copper hydroxide according to claim 9, characterized in that The hollow spherical copper hydroxide comprises a hollow portion, and the hollow portion accounts for 1 / 4.5 to 1 / 3.5 of the total volume of the hollow spherical copper hydroxide.

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