Process for the purification of anhydrous copper chloride

Abstract

The application discloses a purification method of anhydrous copper chloride, which comprises the following steps: mixing industrial basic copper chloride and hydrochloric acid, wherein the mass ratio of the industrial basic copper chloride to hydrogen chloride in the hydrochloric acid is (1.2-3):1, to prepare a first mixed solution; mixing a pH regulator, a relative density regulator and the first mixed solution to prepare a second mixed solution, wherein the pH value of the second mixed solution is 0.5-2.2, and the relative density of the second mixed solution is 1-1.4; mixing the second mixed solution and a decontaminant, adding a pH regulator to prepare a third mixed solution; mixing the third mixed solution and an adsorbent, removing precipitates, adding a pH regulator to prepare a fourth mixed solution; concentrating the fourth mixed solution until solid is precipitated, separating the solid and drying the solid. The pH value and the relative density of the mixture after the reaction of the basic copper chloride and the hydrochloric acid are limited, the reaction is promoted, and the impurity separation is facilitated; the soluble impurities in the precipitate are removed by using the decontaminant, various impurities are removed by using the adsorbent, and high-purity anhydrous copper chloride is obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of inorganic compounds, in particular to a purification method of anhydrous copper chloride. BACKGROUND

[0002] Traditional anhydrous copper chloride is mostly prepared by using copper chloride dihydrate crystals to be heated and dehydrated in a hydrogen chloride atmosphere, but this method has harsh production conditions, high requirements for production equipment, great harm to the environment and operating personnel, and the obtained product is in powder form, which is difficult to promote industrialization.

[0003] Copper chloride dihydrate, as one of the raw materials for preparing anhydrous copper chloride, generally exists in etching waste liquid of circuit board recycling copper. However, in the process of directly using the etching waste liquid as a raw material to prepare copper chloride, ammonium salt and other anion impurities cannot be effectively removed, and metal impurities also affect the purity of copper chloride dihydrate, thereby affecting the purity of subsequent anhydrous copper chloride. If copper chloride dihydrate is prepared by reacting basic copper chloride with hydrochloric acid, and high-purity electronic-grade copper chloride dihydrate is required, then co-precipitation materials need to be introduced, which leads to a large increase in other impurities, and the anhydrous copper chloride obtained by subsequent drying cannot reach high purity. SUMMARY

[0004] Therefore, it is necessary to provide a purification method of high-purity anhydrous copper chloride which reduces harm to the environment and people and is suitable for industrialization.

[0005] An embodiment of the present application provides a purification method of anhydrous copper chloride, comprising the following steps:

[0006] Mixing industrial-grade basic copper chloride and hydrochloric acid, the mass ratio of the industrial-grade basic copper chloride to hydrogen chloride in the hydrochloric acid is (1.2-3): 1, to prepare a first mixed solution;

[0007] Mixing a pH adjuster, a relative density adjuster, and the first mixed solution to prepare a second mixed solution, the pH value of the second mixed solution is 0.5-2.2, and the relative density of the second mixed solution is 1-1.4;

[0008] Mixing the second mixed solution and a decontaminating agent, adding the pH adjuster, to prepare a third mixed solution, the pH value of the third mixed solution is 2-4;

[0009] Mixing the third mixed solution and an adsorbent, removing the precipitate, adding the pH adjuster, to prepare a fourth mixed solution, the pH value of the fourth mixed solution is 0.2-1;

[0010] Concentrating the fourth mixed solution until solids are precipitated, separating the solids, and drying.

[0011] In one of the embodiments, the pH regulator comprises one or both of hydrochloric acid and industrial grade basic copper chloride.

[0012] In one of the embodiments, the relative density regulator comprises one or both of water and the industrial grade basic copper chloride.

[0013] In one of the embodiments, the mixing time of the industrial grade basic copper chloride and the hydrochloric acid is 0.5 hour to 4 hours.

[0014] In one of the embodiments, the mass ratio between the impurity removing agent and the industrial grade basic copper chloride is 1:(50-400).

[0015] In one of the embodiments, the impurity removing agent is hydrogen peroxide.

[0016] In one of the embodiments, the mass ratio between the adsorbent and the industrial grade basic copper chloride is 1:(500-1500).

[0017] In one of the embodiments, the adsorbent comprises activated carbon.

[0018] In one of the embodiments, after mixing the third mixed solution and the adsorbent and before removing the precipitate, it further comprises: keeping at a temperature of 65-85℃ for 1.5-8 hours.

[0019] In one of the embodiments, the drying temperature is 100-130℃ and the drying time is 4-25 hours.

[0020] An embodiment of the present application provides a purification method of anhydrous copper chloride. The pH value and the relative density of the mixture after the reaction of basic copper chloride and hydrochloric acid are limited, which promotes the reaction and facilitates the separation of impurities. The soluble impurities in the raw material are precipitated by using an impurity removing agent, and then various impurities are removed by using an adsorbent, so as to ensure that the solution has high-purity copper chloride. Further, the solution is concentrated to precipitate part of the solid, i.e., copper chloride dihydrate, which plays a role in inducing the growth of crystallization, and finally high-purity anhydrous copper chloride is obtained. The above-mentioned purification method does not need to be heated and dehydrated in a hydrogen chloride atmosphere, which reduces the harm to the environment and people, and also reduces the production process requirements, which is convenient for production and promotion. DETAILED DESCRIPTION

[0021] The application can be implemented in numerous ways, including the described embodiments. Rather, the described embodiments are intended to convey the disclosure content of the application more fully and accurately. They are not intended to limit the application in any way. Further, the application can be implemented in a variety of other ways not specifically described herein. It is also to be understood that the terminology used herein is for the purpose of describing the particular embodiments only and is not intended to be limiting, unless the contrary is indicated.

[0022] Also, the terms "first", "second", and the like, do not denote any ontological limitation, but are used for disambiguation only. The terms "comprising", "containing", "including", "having" and the like, are not intended to exclude that the respective embodiments also comprise, contain, include or have other elements, unless the contrary is indicated. The terms "a" and "an" and "the" and similar reference used in conjunction with an enumeration of a plurality of items to indicate that it is each item of the plurality, are to be understood to encompass only one of the items in the plurality, unless the contrary is indicated.

[0023] All percentages, fractions and ratios are calculated by weight of the total composition, unless otherwise indicated. All amounts expressed in the description of the listed ingredients refer to the content of the active material, and therefore they do not include solvents or by-products that can be contained in the commercially available materials. The term "mass percentage content" can be indicated with the symbol "%".

[0024] "comprising", "containing", "including", "having" or other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises, contains, includes or has an item or a list of items who does not also preclude other similar items or other items not expressly listed or other steps. The term "comprising" is intended to capture the terms "consisting of" and "consisting essentially of". The compositions and methods / processes of the application comprise, consist essentially of and consist of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps or limitations described herein. The terms "efficacy", "performance", "effect", "efficiency" are not distinguished between herein.

[0025] The words "preferred" and "preferably" in this application do not all have a similar connotation. To the extent they can be deemed to have a similar connotation, those terms are used to indicate that a described embodiment is, for certain reasons, a preferred or advantageous embodiment. However, the use of those terms does not imply that all embodiments using any of the features shown in or associated with a preferred embodiment are undesirable. Stated another way, use of the terms "preferred" and "preferably" does not suggest that a described embodiment is required, essential, or one of the only embodiments useful in accordance with the application.

[0026] When a numerical range is disclosed herein, the range is to be construed as having a lower limit and an upper limit, and each integer within the range and fraction of this minimum and maximum. Further, when ranges are provided for a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. Still further, when a feature or characteristic is disclosed in the context of a particular aspect or embodiment, it should be understood that such feature or characteristic can be incorporated into any other aspect or embodiment.

[0027] One embodiment of the present application provides a purification method of anhydrous copper chloride, comprising the following steps:

[0028] Mixing industrial grade basic copper chloride and hydrochloric acid, the mass ratio of the industrial grade basic copper chloride to hydrogen chloride in the hydrochloric acid is (1.2-3) : 1, to prepare a first mixed solution;

[0029] Mixing a pH regulator, a relative density regulator and the first mixed solution to prepare a second mixed solution, the pH value of the second mixed solution is 0.5-2.2, and the relative density of the second mixed solution is 1-1.4;

[0030] Mixing the second mixed solution and a decontaminating agent, adding a pH regulator to prepare a third mixed solution, the pH value of the third mixed solution is 2-4;

[0031] Mixing the third mixed solution and an adsorbent, removing precipitates, adding a pH regulator to prepare a fourth mixed solution, the pH value of the fourth mixed solution is 0.2-1;

[0032] Concentrating the fourth mixed solution to precipitate solids, separating the solids, and drying.

[0033] One embodiment of the present application provides a purification method of anhydrous copper chloride, the limitation of the pH value and the relative density of the mixture after the reaction of basic copper chloride and hydrochloric acid promotes the reaction and facilitates the separation of impurities, the soluble impurities in the raw material are precipitated by using a decontaminating agent, and various impurities are removed by using an adsorbent, so as to ensure that the solution has high-purity copper chloride, further, the concentration to the precipitation of part of solids, i.e. copper chloride dihydrate, plays a role in inducing the growth of crystallization, and finally high-purity anhydrous copper chloride is obtained. The above-mentioned purification method does not need to be heated and dehydrated in a hydrogen chloride atmosphere, reduces the harm to the environment and people, and also reduces the production process requirements, which is convenient for production promotion.

[0034] In one specific example, the composition of the industrial grade basic copper chloride includes, in terms of mass percentage: basic copper chloride ≥98%, ammonium (NH4) <0.3%, iron (Fe) <0.03%, other metals <0.1%, phosphorus <1.0%, and moisture <1.5%.

[0035] In one specific example, the pH adjusting agent includes one or both of hydrochloric acid and industrial grade cupric hydroxide. The relative density adjusting agent includes one or both of water and industrial grade cupric hydroxide.

[0036] It is appreciated that the pH of the second mixture can be adjusted to be 0.6-2 using the pH adjusting agent. Specifically, the pH of the second mixture can be, but is not limited to, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2. The relative density of the second mixture can be adjusted to be 1.0-1.4 using the relative density adjusting agent. Specifically, the relative density of the second mixture can be, but is not limited to, 1.0, 1.1, 1.15, 1.2, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28, 1.29, 1.3, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39 or 1.4.

[0037] In one specific example, the mixing time of the industrial grade cupric hydroxide and the hydrochloric acid is 0.5-4 hours.

[0038] Specifically, the mixing time of the industrial grade cupric hydroxide and the hydrochloric acid can be, but is not limited to, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours, which can facilitate the reaction of the industrial grade cupric hydroxide and the hydrochloric acid.

[0039] In one specific example, the mass ratio between the impurity removing agent and the industrial grade cupric hydroxide is 1:(50-400). Further, the mass ratio between the impurity removing agent and the industrial grade cupric hydroxide is 1:(60-380). Specifically, the mass ratio between the impurity removing agent and the industrial grade cupric hydroxide can be, but is not limited to, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190, 1:200, 1:210, 1:220, 1:230, 1:240, 1:250, 1:260, 1:270, 1:280, 1:290, 1:300, 1:310, 1:320, 1:330, 1:340, 1:350, 1:360, 1:370 or 1:380. The mass of the industrial grade cupric hydroxide defined herein is the mass of the industrial grade cupric hydroxide originally added, and does not include the industrial grade cupric hydroxide added in the process of purification for adjusting the pH or the relative density.

[0040] In one specific example, the impurity removing agent is hydrogen peroxide, and the heating boiling is performed after mixing the hydrogen peroxide impurity removing agent and the second mixed solution. Further, the pH adjusting agent is added to prepare a third mixed solution, and the pH value of the third mixed solution is 2-4. Preferably, the pH value of the third mixed solution is 2.1-3. Specifically, the pH value of the third mixed solution can be, but is not limited to, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.

[0041] In one specific example, the mass ratio between the adsorbent and the industrial grade basic copper chloride is 1: (500-1500). Further, the mass ratio between the adsorbent and the industrial grade basic copper chloride can be, but is not limited to, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1100, 1:1200, 1:1300, 1:1400 or 1:1500. The mass of the industrial grade basic copper chloride defined herein is the mass of the industrial grade basic copper chloride originally added, and does not include the industrial grade basic copper chloride added in the process of purification for adjusting the pH value or the relative density and the like.

[0042] In one specific example, the adsorbent includes activated carbon.

[0043] In one specific example, after mixing the third mixed solution and the adsorbent and before removing the precipitate, the solution is further kept at a temperature of 65-85°C for 1.5-8 hours. Further, the temperature can be, but is not limited to, 65°C, 67°C, 69°C, 71°C, 73°C, 75°C, 77°C, 79°C, 81°C, 83°C or 85°C. Understandably, the solution is kept in a state of micro-boiling at the above-mentioned temperature, and the time for keeping the above-mentioned temperature can be, but is not limited to, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours.

[0044] Further, after removing the precipitate, the pH value of the fourth mixed solution is adjusted to 0.4-0.9 by using the pH adjusting agent. Specifically, the pH value of the fourth mixed solution can be, but is not limited to, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.9.

[0045] In one specific example, the method of concentrating the fourth mixture to precipitate solids can be but is not limited to reduced pressure concentration, and after the precipitation of solids, cooling to 30-45°C, specifically, can be but is not limited to cooling to 30°C, 33°C, 36°C, 39°C, 42°C or 45°C. Understandably, the reduced pressure concentration to a small amount of copper chloride dihydrate crystallization precipitation, increasing the proportion of copper chloride in the solution to play a role in inducing crystal growth, can promote the growth of copper chloride, increase the production efficiency of purification. Compared with the input of copper chloride crystal seeds, it can avoid the solution of the crystal nucleus in the growth of copper chloride solution in the crystalline body, which leads to the increase of the impurity composition of the crystal, and affects the purity of the product.

[0046] In one specific example, the drying temperature is 100-130°C, and the drying time is 4-25 hours. Further, the drying temperature can be but is not limited to 100°C, 105°C, 110°C, 115°C, 120°C, 125°C or 130°C, and the drying time can be but is not limited to 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours or 25 hours.

[0047] Understandably, the compositions of the industrial grade basic copper chloride used in the above-mentioned initially purified industrial grade basic copper chloride, pH adjuster and relative density adjuster can be the same or different, preferably, the compositions of the industrial grade basic copper chloride used in the initially purified industrial grade basic copper chloride, pH adjuster and relative density adjuster are the same.

[0048] The purification method of anhydrous copper chloride of the present application is further described in detail in combination with specific examples. The raw materials used in the following examples, such as no special instructions, are all commercially available products. The industrial grade basic copper chloride used in the following examples and comparative examples is produced by Huizhou TCL Environmental Science and Technology Co., Ltd., batch number 2304062, mass percentage of basic copper chloride is 98.49%, mass percentage of copper is 58.57%.

[0049] Example 1

[0050] In a 3000ml beaker, 300g of pure water was added, 800g of industrial grade basic copper chloride was added under stirring, then 1300g of 31.69% mass fraction hydrochloric acid was added, stirring for 1 hour until the crystallization reaction, then 31.69% mass fraction hydrochloric acid was added to adjust the pH value of the solution to 0.87, pure water was added to adjust the relative density of the solution to 1.24, then 10g of 27.5% mass fraction hydrogen peroxide was added under stirring in three times, heated to boiling, then industrial grade basic copper chloride was added to adjust the pH value to 2.53, 1g of activated carbon was added for adsorption, after 2 hours of 72℃ incubation, the copper chloride clear solution was obtained by filtration. The clear solution was transferred to a 2000ml three-necked round-bottom flask, the pH value was adjusted to 0.65 by adding 31.69% mass fraction hydrochloric acid, heated to concentrate until a small amount of crystals were precipitated in the solution, stopped heating, cooled to 35℃, and then centrifuged to obtain hydrated copper chloride crystalline solid. The hydrated copper chloride crystalline solid was placed in a vacuum drying oven, dried at 110℃ under-0.04MPa negative pressure for 18 hours to obtain anhydrous copper chloride crystals with a purity of 99.60%.

[0051] Example 2

[0052] In a 5000ml beaker, 900g of pure water was added, stirring was started, 2000g of industrial grade basic copper chloride was added, then 2400g of 31.69% mass fraction hydrochloric acid was added, stirring for 3 hours until the crystallization reaction, then 31.69% mass fraction hydrochloric acid was added to adjust the pH value of the solution to 1.94, pure water was added to adjust the relative density of the solution to 1.24, then 20g of 27.5% mass fraction hydrogen peroxide was added under stirring in three times, heated to boiling, then industrial grade basic copper chloride was added to adjust the pH value of the solution to 2.18, 2.5g of activated carbon was added for adsorption, after 2 hours of 75℃ incubation, the copper chloride clear solution was obtained by filtration. The clear solution was transferred to a 2000ml three-necked round-bottom flask, the pH value was adjusted to 0.48 by adding 31.69% mass fraction hydrochloric acid, heated to concentrate until a small amount of crystals were precipitated in the solution, stopped heating, cooled to 35℃, and then centrifuged to obtain hydrated copper chloride crystalline solid. The hydrated copper chloride crystalline solid was placed in a vacuum drying oven, dried at 100℃ under-0.04MPa negative pressure for 21 hours to obtain anhydrous copper chloride crystals with a purity of 99.43%.

[0053] Example 3

[0054] In 5000L reactor kettle synthesis pot, add 900kg pure water, start stirring, add 2000kg industrial grade basic copper chloride, then add 3500kg 31.67% mass fraction hydrochloric acid, stir for 3 hours until crystallization reaction, then add 31.67% mass fraction hydrochloric acid to adjust the pH value of the solution to 0.72, add pure water to adjust the relative density of the solution to 1.29, then add 100kg 27.5% mass fraction hydrogen peroxide to the pot under stirring, heat to boiling, then add industrial grade basic copper chloride to adjust the pH value to 2.95, add 2.5kg activated carbon for adsorption, then heat to 69℃ for 2 hours. After filtration, the copper chloride clear solution is transferred to a 3000L reactor kettle, 40kg hydrochloric acid is added to adjust the pH value to 0.89, heated and concentrated under reduced pressure until a small amount of crystals precipitate from the solution, then stop heating, cool to 30℃, discharge the solution, and centrifuge to obtain hydrated copper chloride crystalline solid. Then, the vacuum rotary dryer is used at -0.04MPa negative pressure and 120℃ for 15 hours to obtain anhydrous copper chloride crystalline with a content of 99.37%.

[0055] Example 4

[0056] In 5000L reactor kettle synthesis pot, add 900kg pure water, start stirring, add 2000kg industrial grade basic copper chloride, then add 3500kg 31.67% mass fraction hydrochloric acid, stir for 3 hours until crystallization reaction, then add 31.67% mass fraction hydrochloric acid to adjust the pH value of the solution to 0.72, add pure water to adjust the relative density of the solution to 1.29, then add 100kg 27.5% mass fraction hydrogen peroxide to the pot under stirring, heat to boiling, then add industrial grade basic copper chloride to adjust the pH value to 2.95, add 2.5kg activated carbon for adsorption, then heat to 69℃ for 2 hours. After filtration, the copper chloride clear solution is transferred to a 3000L reactor kettle, 40kg hydrochloric acid is added to adjust the pH value to 0.89, heated and concentrated under reduced pressure until a small amount of crystals precipitate from the solution, then stop heating, cool to 30℃, discharge the solution, and centrifuge to obtain hydrated copper chloride crystalline solid. Then, the vacuum rotary dryer is used at -0.04MPa negative pressure and 120℃ for 15 hours to obtain anhydrous copper chloride crystalline with a content of 99.37%.

[0057] Comparative Example 1

[0058] In 3000ml beaker, add 300g pure water, start stirring, add 800g of industrial grade basic copper chloride, then add 1300g of 31.69% mass fraction hydrochloric acid, stir for 1 hour until crystallization reaction, then adjust the pH value of the solution to 0.87 by adding 31.69% mass fraction hydrochloric acid, adjust the relative density of the solution to 1.24 by adding pure water, then add 10g of 27.5% mass fraction hydrogen peroxide to the pot under stirring, after heating and boiling, directly add 1g of activated carbon for adsorption, and keep the temperature at 73℃ for 2 hours. Filter to obtain copper chloride clear solution, add 20g of hydrochloric acid to adjust the pH value to 0.45, transfer to a 2000ml three-necked round-bottom flask, heat and concentrate until a small amount of crystals are precipitated, stop heating, cool to 36℃, and centrifuge to obtain hydrated copper chloride crystalline solid. Dry in a vacuum drying oven at -0.04MPa negative pressure and 110℃ for 18 hours to obtain anhydrous copper chloride crystal with a content of 99.25%.

[0059] Comparative Example 2

[0060] In 3000ml beaker, add 300g pure water, start stirring, add 800g of industrial grade basic copper chloride, then add 1300g of 31.69% mass fraction hydrochloric acid, stir for 1 hour until crystallization reaction, then adjust the pH value of the solution to 0.87 by adding 31.69% mass fraction hydrochloric acid, adjust the relative density of the solution to 1.24 by adding pure water, then add 10g of 27.5% mass fraction hydrogen peroxide to the pot under stirring, after heating and boiling, directly add 1g of activated carbon for adsorption, and keep the temperature at 73℃ for 2 hours. Filter to obtain copper chloride clear solution, transfer to a 2000ml three-necked round-bottom flask, heat and concentrate until a small amount of crystals are precipitated, stop heating, cool to 36℃, and centrifuge to obtain hydrated copper chloride crystalline solid. Dry in a vacuum drying oven at -0.04MPa negative pressure and 110℃ for 18 hours to obtain anhydrous copper chloride crystal with a content of 99.25%.

[0061] Comparative Example 3

[0062] In 3000ml beaker, 300g pure water, under stirring, add 800g industrial grade basic copper chloride, then add 1300g of 31.69% mass fraction hydrochloric acid, stirring for 1 hour until the crystallization reaction, add 31.69% mass fraction hydrochloric acid to adjust the pH value of the solution to 1.02, add pure water to adjust the relative density of the solution to 1.43, then add 10g of 27.5% mass fraction hydrogen peroxide under stirring, heat and boil, then add industrial grade basic copper chloride to adjust the pH value to 2.24, add 1g activated carbon for adsorption, keep at 75℃ for 2 hours, then filter to obtain copper chloride clear solution. Add 31.69% mass fraction hydrochloric acid to the clear solution to adjust the pH value to 0.53, transfer to a 2000ml three-necked round-bottom flask, heat and concentrate until a small amount of crystals are precipitated, stop heating, cool to 35℃, and centrifuge to obtain hydrated copper chloride crystalline solid. Place the hydrated copper chloride crystalline solid in a vacuum drying oven, use negative pressure-0.04MPa, dry at 110℃ for 18 hours to obtain anhydrous copper chloride crystals with a purity of 98.25%.

[0063] The impurity content in the anhydrous copper chloride products obtained in the examples and comparative examples was measured, and the measurement results are shown in Table 1 below:

[0064] Table 1

[0065]

[0066] It should be noted that in the measurement of the purified components, since the purified product contains moisture and some unknown impurities, and the main product anhydrous copper chloride is easy to absorb water, the determination method of anhydrous copper chloride is titration, which cannot achieve the accuracy of the measurement of other metals, resulting in the total content of the final product not reaching 100%, which is not a mistake in the test data.

[0067] The above test method for water insoluble matter of hydrated copper chloride intermediate before drying is as follows: take 20g sample, dissolve in 150ml hot water, add 1ml of 37% reagent hydrochloric acid, heat in water bath for 1h, and measure according to the provisions of GB / T 9738; the above test method for water insoluble matter of anhydrous copper chloride is as follows: take 20g sample, dissolve in 150ml hot water, add 1ml of 37% reagent hydrochloric acid, heat in water bath for 1h, filter with a 4# glass filter pot that has been kept at 105℃±2℃, wash the residue with hot water until the washing liquid is colorless, dry in an electric oven at 105℃±2℃ until constant weight, and the results are calculated according to the provisions of GB / T 9738-2008.

[0068] Through the product content analysis of the above-mentioned examples and comparative examples, the pH value is not adjusted in the heat preservation and impurity removal stage of the process of comparative example 1, so that the iron is not relatively precipitated, resulting in high iron content in the product anhydrous copper chloride. The pH value is not adjusted during concentration in the process of comparative example 2, and the intermediate product hydrated copper chloride before drying is dissolved (50g of crystals are dissolved in 70ml of pure water), the turbidity is tested to be 356NTU, the solution after dissolution is relatively turbid, the final product anhydrous copper chloride is dissolved, and there is a phenomenon of insoluble sediment, and the impurities are more. The relative density 1.43 is adjusted in the heat preservation and impurity removal stage of the process of comparative example 3, and the process filtration of copper chloride clear liquid is difficult, the filtration is slow, and there is a risk of insoluble filtration, the intermediate product hydrated copper chloride before drying is dissolved (50g of crystals are dissolved in 70ml of pure water), the turbidity is tested to be 73NTU, the product anhydrous copper chloride has high iron impurities, and the impurity removal effect is poor. It can be seen that the anhydrous copper chloride purified by example 1 to example 4 has high purity and less impurities.

[0069] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0070] The technical features of the above examples can be combined in any way, and for the sake of brevity, not all possible combinations are described, however, any combination of the technical features is deemed to be within the scope of the present disclosure.

[0071] The above-described examples only express several embodiments of the present application, facilitate specific and detailed understanding of the technical solutions of the present application, but cannot be understood as limiting the scope of patent protection. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. It should be understood that the technical solutions obtained by the skilled person in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present application are within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application should be based on the content of the appended claims, and the description can be used to explain the content of the claims.

Claims

1. A method for purifying anhydrous copper chloride, characterized by, The method comprises the following steps: mixing industrial-grade basic copper chloride with hydrochloric acid, the mass ratio of the industrial-grade basic copper chloride to hydrogen chloride in the hydrochloric acid being (1.2-3): 1, to prepare a first mixed solution; mixing a pH regulator, a relative density regulator and the first mixed solution to prepare a second mixed solution, the pH value of the second mixed solution being 0.5-2.2, and the relative density of the second mixed solution being 1-1.4; mixing the second mixed solution with a decontaminant, the decontaminant being hydrogen peroxide, and adding the pH regulator to prepare a third mixed solution, the pH value of the third mixed solution being 2-4; mixing the third mixed solution with an adsorbent, removing precipitates, and adding the pH regulator to prepare a fourth mixed solution, the pH value of the fourth mixed solution being 0.2-1; concentrating the fourth mixed solution until solids are precipitated, separating the solids, and drying.

2. The purification method of anhydrous copper chloride according to claim 1, characterized by, The pH regulator comprises one or both of hydrochloric acid and industrial-grade basic copper chloride.

3. The purification method of anhydrous copper chloride according to claim 1, characterized by, The relative density regulator comprises one or both of water and the industrial-grade basic copper chloride.

4. The purification method of anhydrous copper chloride according to claim 1, characterized by, The mixing time of the industrial-grade basic copper chloride and the hydrochloric acid is 0.5 hours-4 hours.

5. The purification method of anhydrous copper chloride according to claim 1, characterized by, The mass ratio between the decontaminant and the industrial-grade basic copper chloride is 1:(50-400).

6. The purification method of anhydrous copper chloride according to claim 1, characterized by, The mass ratio between the adsorbent and the industrial-grade basic copper chloride is 1:(500-1500).

7. The purification method of anhydrous copper chloride according to claim 1, characterized by, The adsorbent comprises activated carbon.

8. The purification method of anhydrous copper chloride according to any one of claims 1 to 7, characterized by, After mixing the third mixed solution with the adsorbent and before removing the precipitates, the method further comprises keeping the mixture at a temperature of 65-85℃ for 1.5 hours-8 hours.

9. The purification method of anhydrous copper chloride according to any one of claims 1 to 7, characterized by, The drying temperature is 100-130℃, and the drying time is 4-25 hours.

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