A method for preparing refined cuprous chloride

Abstract

The application discloses a preparation method of refined cuprous chloride, which comprises the following steps: preparing an oxygen-containing copper compound into refined cuprous chloride, wherein the method does not need high-purity copper salt compared with the existing wet process, so that the production cost is low; in addition, the method further introduces a protective agent and a reducing agent to coordinate with each other, so that the product purity is higher than that of the existing process; in addition, the method does not involve waste liquid, and the recovered liquid can be reused, so that the process flow is short, safe and environmentally friendly.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of inorganic chemistry, and particularly relates to a preparation method of cuprous chloride. BACKGROUND

[0002] At present, the preparation method of cuprous chloride is roughly divided into dry method and wet method. The dry method is to heat and melt copper powder, pass chlorine gas into the copper powder, air dry the generated cuprous chloride melt, crush and bag. The disadvantage of this process is that the purity of the prepared copper source is required to be very high, and the air humidity and oxygen influence on the cuprous chloride cannot be guaranteed in the air drying process, thereby reducing the content of monovalent copper and failing to meet the standard of refined cuprous chloride.

[0003] The wet method is to dissolve copper / copper oxide in concentrated hydrochloric acid, and then add copper powder and a reducing agent to the solution to prepare cuprous chloride. The disadvantage of this method is that the mixed solution of concentrated hydrochloric acid and sodium chloride has strong corrosion in the preparation process, the dissolution process is slow, the introduction of sodium ions reduces the purity, and the addition of copper powder and a reducing agent also needs to be accurately controlled, otherwise, divalent copper or copper powder mixed into the product will also cause low purity of cuprous chloride. SUMMARY

[0004] The purpose of the present application is to overcome the shortcomings of the prior art, and provide a preparation method of cuprous chloride, which has low production cost, high product purity, short process flow, safety and environmental protection, and high product purity.

[0005] The present application is achieved by the following technical solutions:

[0006] A preparation method of cuprous chloride comprises the following steps:

[0007] Step 1, slowly add an oxygen-containing copper compound to dilute hydrochloric acid under stirring to obtain a first mixture, and adjust the pH value of the first mixture to 1.5-2; continue stirring for 30-60 min, and then perform solid-liquid separation to obtain a first solid and a first liquid which enters step 2;

[0008] The mass ratio of the oxygen-containing copper compound to dilute hydrochloric acid is 1:1-3;

[0009] Step 2, add a protective agent to the first liquid obtained in step 1, stir for 1-2 h, then heat to 200-250 DEG C, add a reducing agent, and continue to stir for 1-2 h to obtain a second mixture;

[0010] The protective agent is a mixture of N,N-dimethylformamide (DMF) and o-phenanthroline, and the molar ratio of N,N-dimethylformamide (DMF) to o-phenanthroline is 5-10:1;

[0011] The protective agent is used in an amount of 1-2 times the mass of the oxygen-containing copper compound in step 1.

[0012] The reducing agent is at least one of ascorbic acid or hydroxylamine hydrochloride.

[0013] The reducing agent is used in an amount of 0.5-2 times the mass of the oxygen-containing copper compound in step 1.

[0014] Step 3: The second mixture is cooled to -10-30℃ and kept for 4-8 hours to obtain a third mixture.

[0015] The third mixture is subjected to solid-liquid separation in an air-excluded state to obtain a solid part as a second solid and a liquid part as a second liquid.

[0016] Step 4: The second solid obtained in step 3 is washed and dried to obtain refined cuprous chloride.

[0017] In the above technical solution, the oxygen-containing copper compound is one or more of copper oxide, cuprous oxide, copper hydroxide or copper carbonate.

[0018] In the above technical solution, in step 1, the pH of the first mixture is adjusted by adding dilute hydrochloric acid to the first mixture.

[0019] In the above technical solution, in step 1, the mass ratio of the oxygen-containing copper compound to dilute hydrochloric acid is 1:3.

[0020] In the above technical solution, the concentration of the dilute hydrochloric acid is 1-3 mol / L.

[0021] In the above technical solution, in step 3, the second liquid obtained is recovered and used to prepare dilute sulfuric acid.

[0022] In the above technical solution, the solid-liquid separation process is carried out by filtration.

[0023] In the above technical solution, the solid-liquid separation in the air-excluded state is carried out under the protection of nitrogen or inert gas.

[0024] In step 1-3, the reaction in the reaction kettle is allowed to contact only a small amount of air in the kettle, and in step 2, the protective agent and the reducing agent have the effect of protecting monovalent copper from being oxidized to divalent copper by oxygen in the air in the kettle. The protective agent is in the liquid phase during solid-liquid separation (filtration), and the final product needs to be in the solid phase, so air needs to be excluded during the solid-liquid separation process.

[0025] In the above technical solution, in step 4, the second solid is washed with an organic solvent.

[0026] The organic solvent is a mixture of ethanol and petroleum ether, and the amount is 1-5 times of the mass of the oxygen-containing copper compound.

[0027] The organic solvent is a mixture of ethanol and petroleum ether, and the mass ratio is 1:1-5.

[0028] The steps 1-3 are performed in a enamel reaction kettle.

[0029] The present application has the following advantages and beneficial effects:

[0030] The oxygen-containing copper compound is prepared into refined cuprous chloride, and the present process has lower production cost than the existing wet process because it does not need high-purity copper salt. In addition, the present process introduces a protective agent and a reducing agent to coordinate with each other, so that the product purity is higher than that of the existing process. The content of the refined cuprous chloride is higher than 99%. Furthermore, the present process does not involve waste liquid, and the recovered liquid can be reused, so that the process flow is short, safe and environmentally friendly. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 The FTIR spectrum of the refined cuprous chloride obtained in Example 1 is compared with the standard spectrum library.

[0032] Figure 2 The SEM electron microscope image of the refined cuprous chloride obtained in Example 1 is shown.

[0033] Figure 3 The sample element analysis result of the refined cuprous chloride obtained in Example 1 is shown.

[0034] Figure 4 The XRD spectrum of the refined cuprous chloride obtained in Example 1 is compared with the standard card.

[0035] Figure 5 The particle size analysis graph of the refined cuprous chloride obtained in Example 1 is shown.

[0036] Figure 6 The weight loss curve of the refined cuprous chloride obtained in Example 1 in air and nitrogen atmosphere is shown.

[0037] Figure 7 The specific surface area curve of the refined cuprous chloride obtained in Example 1 is shown.

[0038] Figure 8 The physical adsorption curve of the refined cuprous chloride obtained in Example 1 is shown.

[0039] For those skilled in the art, other related drawings can be obtained from the above drawings without creative labor. DETAILED DESCRIPTION

[0040] In order to make the person skilled in the art better understand the technical scheme of the present application, the technical scheme of the present application is further illustrated below in combination with specific examples.

[0041] Example 1

[0042] Step 1, add 200g of 1mol / L dilute hydrochloric acid to the enamel reaction kettle, start stirring, slowly add 200g of copper oxide to the reaction kettle, then continue to slowly add dilute hydrochloric acid to the kettle to adjust the PH of the kettle liquid to 1.5, continue to stir for 30min, then filter the reaction product of this step, and return the filtrate to the reaction kettle;

[0043] Step 2, continue to add 200g of protective agent (DMF and o-phenanthroline in a molar ratio of 5:1) to the reaction kettle, stir for 1h, then heat the reaction kettle to 200℃, add 100g of ascorbic acid to the kettle, continue to stir for 1h,

[0044] Step 3, cool the kettle liquid to -10℃, keep for 4h, then filter in an air-tight manner, and the filtrate can be recycled for dilute hydrochloric acid preparation.

[0045] Step 4, wash the filtered crystals with 200g of organic solvent (ethanol and petroleum ether in a mass ratio of 1:5), the washed organic solvent can be recycled, and the washed crystals are refined cuprous chloride, which is sealed and stored in the sun after vacuum drying, and the purity of the refined cuprous chloride is 99.15% according to the national standard HG / T-2960-2010.

[0046] Example 2

[0047] Step 1, add 500g of 2mol / L dilute hydrochloric acid to the enamel reaction kettle, start stirring, slowly add 250g of cuprous oxide to the reaction kettle, then continue to slowly add dilute hydrochloric acid to the kettle to adjust the PH of the kettle liquid to 1.7, continue to stir for 45min, then filter the reaction product of this step, and return the filtrate to the reaction kettle;

[0048] Step 2, continue to add 250g of protective agent (DMF and o-phenanthroline in a molar ratio of 7.5:1) to the reaction kettle, stir for 1.5h, then heat the reaction kettle to 225℃, add 250g of ascorbic acid to the kettle, continue to stir for 1.5h,

[0049] Step 3, cool the kettle liquid to -20℃, keep for 6h, then filter in an air-tight manner, and the filtrate can be recycled for dilute hydrochloric acid preparation.

[0050] Step 4, the crystals are filtered and rinsed with 500g of organic solvent (ethanol and petroleum ether in a mass ratio of 1:2.5), the rinsing organic solvent can be recycled, the washed crystals are refined cuprous chloride, and the refined cuprous chloride is vacuum dried, sealed, and stored in the shade. According to the national standard HG / T-2960-2010, the purity of the refined cuprous chloride is 99.30%.

[0051] Example 3

[0052] Step 1, 1000g of 2mol / L dilute hydrochloric acid is added to a porcelain reaction kettle, stirring is started, 333g of copper hydroxide is slowly added to the reaction kettle, then dilute hydrochloric acid is continuously slowly added to the kettle to adjust the pH of the kettle liquid to 2.0, and stirring is continued for 60min, then the reaction product of this step is filtered, and the filtrate is returned to the reaction kettle;

[0053] Step 2, 666g of the protective agent (DMF and o-phenanthroline in a molar ratio of 10:1) is continuously added to the reaction kettle, stirring is continued for 2h, then the reaction kettle is heated to 250℃, 666g of ascorbic acid is added to the kettle, and stirring is continued for 2h,

[0054] Step 3, the kettle liquid is cooled to -30℃, and kept for 8h, then filtered in an air-tight manner, and the filtrate can be recycled for dilute hydrochloric acid preparation.

[0055] Step 4, the crystals are filtered and rinsed with 1665g of organic solvent (ethanol and petroleum ether in a mass ratio of 1:1), the rinsing organic solvent can be recycled, the washed crystals are refined cuprous chloride, and the refined cuprous chloride is vacuum dried, sealed, and stored in the shade. According to the national standard HG / T-2960-2010, the purity of the refined cuprous chloride is 99.33%.

[0056] The refined cuprous chloride obtained in Example 1 is subjected to characterization analysis:

[0057] The CuCl content is greater than or equal to 99% and the CuCl2 content is less than or equal to 0.6% according to the national standard HG / T 2960-2010.

[0058] The analysis instruments used are as follows:

[0059] EDS energy spectrum; XRD X-ray diffractometer; ICP-OES inductively coupled plasma emission spectrometer; FTIR Fourier transform infrared spectrometer; GC-2014C gas chromatograph; Mastersizer 3000E laser particle size instrument; ASAP2460 dual-station specific surface area and pore size analyzer of American Micromeritics; Karl Fischer moisture analyzer; ultraviolet spectrophotometer; and HG / T-2960-2010 national standard analysis method.

[0060] The FTIR analysis results are as follows: Figure 1From the infrared spectrum analysis, it can be seen that the sample is mainly CuCl, which is basically consistent with the CuCl standard picture.

[0061] The SEM image is shown in Figure 2 , and the sample element analysis result is shown in Figure 3 ; from the SEM picture and the element analysis result, it can be seen that the sample has high purity, and the main components are Cu and Cl elements.

[0062] The XRD analysis result is shown in Figure 4 , and the sample half-peak width data is shown in Table 1 below; the sample has typical cuprous chloride crystal diffraction peaks, and the average crystal size is about 62 nm.

[0063] Table 1. Half-peak width data of the sample

[0064]

[0065] Note: hlk represents the crystal face, FWHM represents the half-height width, , and the grain size unit is angstrom, 1 angstrom = 0.1 nm

[0066] The ICPOES analysis result of the sample is shown in Table 2 below, from which it can be seen that the sample has high purity, and the content of elements such as Al, Fe, K, Mg, Na, Si, etc. is less than 100 ppm.

[0067] Table 2. ICPOES analysis result

[0068]

[0069]

[0070] The particle size analysis of the sample is shown in Figure 5 , from which it can be seen that the average particle size of the sample is 85.5 μm.

[0071] The thermal gravimetric analysis of the sample is shown in Figure 6 , and the weight loss curve of the sample under air and nitrogen atmosphere can be obtained. The sample has less weight loss before 426℃, and the weight loss increases after 426℃, because the melting point of CuCl is 426℃, and the molten sample is carried away by the protective gas, indicating that the product cuprous chloride has high purity.

[0072] The specific surface area analysis of the sample is shown in Figure 7 , and the physical adsorption analysis of the sample is shown in Figure 8 ; the specific surface area of the sample is 0.2448±0.0017m 2 / g.

[0073] The moisture content of the sample is 0.262% by Karl Fischer moisture analyzer.

[0074] The sample was analyzed according to the national standard analysis method HG / T-2960-2010, and the experimental results SO4 2- , NO3 - content were all lower than 10 ppm.

[0075] The Cu 2+ was analyzed by ultraviolet spectrophotometry, and the sample Cu 2+ was analyzed according to the method of configuring different concentration Cu ion standard series, and the experimental results were calculated, and the Cu 2+ content was 0.288%.

[0076] The detection results are as follows:

[0077]

[0078]

[0079] The relational terms such as "first" and "second" and the like are merely used to distinguish one from another of the same named components, without necessarily requiring or implying any such actual relationship or order between such components.

[0080] The above has made the exemplary description to the application, should indicate that, in not departing from the core of the application, any simple modification, change or other equivalent replacement which the person skilled in the art can not spend the creative labor falls into the protection scope of the application.

Claims

1. A method for preparing cuprous chloride, characterized in that, Includes the following steps: Step 1: Slowly add an oxygen-containing copper compound to dilute hydrochloric acid while stirring to obtain a first mixture, and adjust the pH of the first mixture to 1.5-2; Continue stirring for 30-60 minutes, then perform solid-liquid separation to obtain the first solid and the first liquid, and proceed to step 2. In step 1, the method for adjusting the pH value of the first mixture is to add dilute hydrochloric acid to the first mixture. The mass ratio of the oxygen-containing copper compound to the dilute hydrochloric acid is 1:1 to 3. Step 2: Add a protective agent to the first liquid obtained in Step 1, stir for 1-2 hours, then heat to 200-250°C, add a reducing agent, and continue stirring for 1-2 hours to obtain the second mixture; The protective agent is a mixture of N,N-dimethylformamide and o-phenanthroline, wherein the molar ratio of N,N-dimethylformamide to o-phenanthroline is 5 to 10:1; The amount of the protective agent is 1 to 2 times the mass of the oxygen-containing copper compound in step 1; The reducing agent is at least one of ascorbic acid or hydroxylamine hydrochloride; The amount of the reducing agent is 0.5 to 2 times the mass of the oxygen-containing copper compound in step 1; Step 3: Cool the second mixture to -10℃ to -30℃ and keep it at that temperature for 4 to 8 hours to obtain the third mixture; The third mixture is subjected to solid-liquid separation in the absence of air to obtain a solid portion as a second solid and a liquid portion as a second liquid. Steps 1 to 3 are all carried out in an enamel-lined reactor. Step 4: Wash the second solid obtained in Step 3 and dry it to obtain refined cuprous chloride.

2. The method for preparing cuprous chloride according to claim 1, characterized in that, The oxygen-containing copper compound is one or more of copper oxide, cuprous oxide, copper hydroxide, or copper carbonate.

3. The method for preparing cuprous chloride according to claim 1, characterized in that, In step 1, the mass ratio of the oxygen-containing copper compound to the dilute hydrochloric acid is 1:

3. The concentration of the dilute hydrochloric acid is 1–3 mol / L.

4. The method for preparing cuprous chloride according to claim 1, characterized in that, In step 3, the second liquid obtained is recycled and used to prepare dilute sulfuric acid.

5. The method for preparing cuprous chloride according to claim 1, characterized in that, The solid-liquid separation process is carried out by filtration.

6. The method for preparing cuprous chloride according to claim 1, characterized in that, The solid-liquid separation process described above is performed under the protection of nitrogen or inert gas.

7. The method for preparing cuprous chloride according to claim 1, characterized in that, In step 4, the second solid is washed with an organic solvent.

8. The method for preparing cuprous chloride according to claim 7, characterized in that, The organic solvent is a mixture of ethanol and petroleum ether, and the amount of organic solvent used is 1 to 5 times the mass of the oxygen-containing copper compound; the organic solvent is a mixture of ethanol and petroleum ether in a mass ratio of 1:1 to 5.

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