阅读说明：本技术 一种高浓度卤化银溶液及其制备方法与卤化银的再生方法 (High-concentration silver halide solution, preparation method thereof and regeneration method of silver halide ) 是由 张金明 万纪强 张军 于 2019-02-28 设计创作，主要内容包括：本发明公开了一种高浓度卤化银溶液及其制备方法与卤化银的再生方法。所述高浓度卤化银溶液包括卤化银和离子液体,所述卤化银在所述溶液中的质量浓度为13-50％。在无酸、无氨、无氰化物的条件下,本发明出人意料地通过使用离子液体,首次直接实现卤化银的溶解,制得高浓度卤化银溶液；该溶液在水、醇等沉淀剂中即可再生。该高浓度卤化银溶液的制备方法及卤化银的再生方法过程简单、高效、环境友好。(The invention discloses a high-concentration silver halide solution, a preparation method thereof and a regeneration method of silver halide. The high-concentration silver halide solution comprises silver halide and ionic liquid, and the mass concentration of the silver halide in the solution is 13-50%. Under the conditions of no acid, no ammonia and no cyanide, the invention surprisingly realizes the dissolution of silver halide directly for the first time by using the ionic liquid to prepare a high-concentration silver halide solution; the solution can be regenerated in precipitating agent such as water and alcohol. The preparation method of the high-concentration silver halide solution and the regeneration method of the silver halide have simple processes, high efficiency and environmental protection.)

1. A high-concentration silver halide solution, which is characterized by comprising silver halide and ionic liquid, wherein the mass concentration of the silver halide in the solution is 13-50%.

2. The high concentration silver halide solution according to claim 1, further comprising an organic solvent;

preferably, the organic solvent is selected from at least one of N, N-dimethyl sulfoxide (DMSO), N '-Dimethylformamide (DMF), N' -dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Methylimidazole (N-Methylimidazole), and Imidazole (Imidazole);

preferably, the silver halide is at least one of silver chloride, silver bromide and silver iodide.

3. The high-concentration silver halide solution according to claim 1 or 2, wherein the ionic liquid is a molten salt of imidazolium cations and/or pyridinium cations with anions, the imidazolium cations and/or pyridinium cations being substituted or unsubstituted;

preferably, the substituent on the imidazolium cation and/or pyridinium cation is C_1-12Alkyl radical, C_1-12At least one alkenyl group.

4. The high concentration silver halide solution according to any one of claims 1 to 3, wherein the ionic liquid is selected from the group consisting of, but not limited to, at least one of the following ionic liquids: 1-ethyl-3-methylimidazolium chloride ionic liquid (EmimCl), 1-ethyl-3-methylimidazolium bromide ionic liquid (EmimBr), 1-allyl-3-methylimidazolium chloride ionic liquid (AmimCl), 1-allyl-3-methylimidazolium bromide ionic liquid (AmimBr), 1-butyl-3-methylimidazolium chloride ionic liquid (BmimCl), 1-butyl-3-methylimidazolium bromide ionic liquid (BmimBr), 1-ethyl-3-methylimidazolium acetate ionic liquid (Emimaac), 1-allyl-3-methylimidazolium acetate ionic liquid (Amimaac), 1-butyl-3-methylimidazolium acetate ionic liquid (Bmimic), N-ethylpyridinium chloride ionic liquid ([ EPy ] Cl), N-ethylpyridine bromide ionic liquid ([ EPy ] Br), 1, 3-dimethylimidazole dimethyl phosphate ionic liquid ([ Dmim ] [ DMP ]), 1-ethyl-3-methylimidazole diethyl phosphate ionic liquid ([ Emim ] [ DEP ]), 3-methylimidazole formate ionic liquid ([ Mim ] [ HCOO ]), N-methylpyridine formate ionic liquid ([ MPy ] [ HCOO ]), 1-ethyl-3-methylimidazole formate ionic liquid ([ Emim ] [ HCOO ]), and 1-butyl-3-methylimidazole formate ionic liquid ([ Bmim ] [ HCOO ]).

5. The method of preparing a high concentration silver halide solution according to any one of claims 1 to 4, comprising the steps of: adding silver halide into ionic liquid and/or ionic liquid/organic solvent mixed solvent, stirring and dissolving to obtain high-concentration silver halide solution.

6. The method for producing a high-concentration silver halide solution according to claim 5, wherein the ionic liquid/organic solvent mixed solvent is a mixed solvent obtained by mixing an ionic liquid and an organic solvent in a mass ratio of 1 (0.01-20);

preferably, the ionic liquid has the meaning as defined in claim 3 or 4 and the organic solvent has the meaning as defined in claim 2.

7. The method for producing a high-concentration silver halide solution according to claim 5 or 6, wherein the mass ratio of the silver halide to a liquid (the liquid is the ionic liquid and/or the mixed solvent of the ionic liquid/organic solvent) is (0.15-1.0): 1.

8. The method for preparing a high concentration silver halide solution according to any one of claims 5 to 7, wherein the stirring time is 20min to 4 h.

9. The method for producing a high-concentration silver halide solution according to any one of claims 5 to 8, wherein the dissolution temperature is 25 to 150 ℃.

10. A silver halide solution obtained by the production method according to any one of claims 5 to 9.

Technical Field

The invention belongs to the fields of metal smelting and green chemistry, and relates to a high-concentration silver halide solution, a preparation method thereof and a regeneration method of silver halide.

Background

Silver halides include silver chloride, silver bromide, and silver iodide, are extremely insoluble in water and common solvents, and are commonly used to detect the presence of silver ions and halide ions. Silver halide dissolution usually requires ammonia, cyanide or a specific concentrated acid solution to be achieved. Highly concentrated solutions (concentrations above 10 wt%) of silver halide are more difficult to obtain due to their poor solubility.

The silver halide exists in the nature and is one of natural silver ores (such as the main component of the ceratitis ore is silver chloride); but also can be directly used in the fields of antibiosis, biomedicine, artificial rainfall, sensitization and the like, and has important practical value. Therefore, the development of a green, environment-friendly, simple and feasible solvent and method for dissolving silver halide is of great significance to the utilization and development of silver halide and the smelting of natural silver ore.

Disclosure of Invention

The present invention provides a high-concentration silver halide solution comprising: silver halide and ionic liquid, the silver halide in the solution of mass concentration of 13-50%, for example the mass concentration can be 15-45%, 20-40%, as an example, the mass concentration can be 15%, 20%, 35%, 45%.

According to the high-concentration silver halide solution, an organic solvent can be contained in the solution; for example, the organic solvent may be selected from: at least one of N, N-dimethyl sulfoxide (DMSO), N '-Dimethylformamide (DMF), N' -dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-Methylimidazole (N-Methylimidazole), Imidazole (Imidazole), and the like.

According to the high concentration silver halide solution of the present invention, the silver halide may be at least one of silver chloride, silver bromide and silver iodide; illustratively, the silver halide may be silver chloride, silver bromide, silver iodide, silver chloride/silver bromide mixtures, silver chloride/silver iodide mixtures, silver bromide/silver iodide mixtures, silver chloride/silver bromide/silver iodide mixtures.

According to the high-concentration silver halide solution, the ionic liquid can be a molten salt formed by imidazole cations and/or pyridine cations and anions, and the imidazole cations and/or the pyridine cations can be substituted or unsubstituted. For example, the substituent on the imidazolium cation and/or pyridinium cation may be C_1-12Alkyl radical, C_1-12At least one of alkenyl and the like; preferably, the substituents may be selected from C_1-6Alkyl radical, C_1-6At least one of alkenyl and the like; asFor example, the substituent may be methyl, ethyl, butyl, allyl. The anion may be at least one of a halogen ion, an alkyl acid ion (e.g., at least one of a formate ion, an acetate ion, etc.), an organophosphate ion (e.g., at least one of an alkyl phosphate ion, a dialkyl phosphate ion, etc.), and the like; for example, the anion may be selected from at least one of halide ion, bromide ion and acetate ion.

Illustratively, the ionic liquid may be selected from at least one of the following ionic liquids, including but not limited to: 1-ethyl-3-methylimidazolium chloride ionic liquid (EmimCl), 1-ethyl-3-methylimidazolium bromide ionic liquid (EmimBr), 1-allyl-3-methylimidazolium chloride ionic liquid (AmimCl), 1-allyl-3-methylimidazolium bromide ionic liquid (AmimBr), 1-butyl-3-methylimidazolium chloride ionic liquid (BmimCl), 1-butyl-3-methylimidazolium bromide ionic liquid (BmimBr), 1-ethyl-3-methylimidazolium acetate ionic liquid (Emimaac), 1-allyl-3-methylimidazolium acetate ionic liquid (Amimaac), 1-butyl-3-methylimidazolium acetate ionic liquid (Bmimic), N-ethylpyridinium chloride ionic liquid ([ EPy ] Cl), N-ethylpyridine bromide ionic liquid ([ EPy ] Br), 1, 3-dimethylimidazole dimethyl phosphate ionic liquid ([ Dmim ] [ DMP ]), 1-ethyl-3-methylimidazole diethyl phosphate ionic liquid ([ Emim ] [ DEP ]), 3-methylimidazole formate ionic liquid ([ Mim ] [ HCOO ]), N-methylpyridine formate ionic liquid ([ MPy ] [ HCOO ]), 1-ethyl-3-methylimidazole formate ionic liquid ([ Emim ] [ HCOO ]), and 1-butyl-3-methylimidazole formate ionic liquid ([ Bmim ] [ HCOO ]).

According to the high-concentration silver halide solution of the present invention, water may be further contained in the silver halide solution.

According to exemplary silver halide solutions of the present invention, the silver halide solution may be an AgCl/AmimCl solution, an AgBr/BmimAc solution, an AgI/AmimCl solution, an AgCl/AgBr/EmimCl solution, an AgCl/AgBr/AgI/AmimCl solution, an AgCl/AmimCl/Min solution, an AgBr/Bmimac/NMP solution, an AgCl/AmimCl/BmimAc/NMP solution.

The invention also provides a preparation method of the high-concentration silver halide solution, which comprises the following steps: adding silver halide into ionic liquid and/or ionic liquid/organic solvent mixed solvent, stirring and dissolving to obtain high-concentration silver halide solution.

According to the preparation process of the present invention, the silver halide has the meaning as described above.

According to the preparation process of the present invention, the ionic liquid has the meaning as described above.

According to the preparation process of the present invention, the organic solvent has the meaning as described above.

According to the preparation method, the ionic liquid/organic solvent mixed solvent can be a mixed solvent obtained by mixing an ionic liquid and an organic solvent according to a mass ratio of 1 (0.01-20); for example, the mass ratio of the ionic liquid to the organic solvent in the ionic liquid/organic solvent mixed solvent can be 1 (0.01-10), 1 (0.01-4), 1 (0.1-3.5) and 1 (0.5-3); as an example, the mass ratio may be 1:1.4, 1:1.5, 1: 2.2. Wherein the ionic liquid has the meaning as described above.

According to the production method of the present invention, the mass ratio of the silver halide to the liquid (the liquid may be the ionic liquid and/or the ionic liquid/organic solvent mixed solvent) may be (0.15 to 1.0):1, for example, the mass ratio may be (0.15 to 0.5):1, (0.2 to 0.45): 1; as an example, the mass ratio may be 0.15:1, 0.2:1, 0.35:1, 0.45: 1.

According to the preparation method of the present invention, the stirring time may be 20min to 4h, for example 30min to 3h, and as an example, the stirring time may be 30min, 1h, 2 h.

According to the preparation method of the present invention, the dissolution temperature is 25 to 150 ℃, for example 50 to 130 ℃, 70 to 120 ℃; as an example, the dissolution temperature may be 80 ℃, 100 ℃, 120 ℃.

According to the preparation method of the invention, the mass concentration of the silver halide solution is 13-50%, such as 15-45%; as an example, the mass concentration may be 15%, 20%, 35%, 45%.

The invention also provides the silver halide solution obtained by the preparation method.

Further, the invention also provides a method for regenerating silver halide in the silver halide solution, wherein a precipitator is added into the silver halide solution, and the regenerated silver halide is obtained by stirring; the precipitant may be selected from at least one of water, ethanol, and methanol. For example, the amount of the precipitant can be selected by one skilled in the art as needed, such as adding the precipitant while stirring until no more precipitate is formed.

The invention has the beneficial effects that:

under the conditions of no acid, no ammonia and no cyanide, the method provided by the invention unexpectedly utilizes an ionic liquid (especially an ionic liquid containing halide ions and carboxylate ions) to directly dissolve the insoluble silver halide, so as to prepare a high-concentration silver halide solution for the first time, the silver halide solution has good solubility, the solution is clear and transparent, and the silver halide concentration is obviously higher than that of the prior art (the mass concentration of the silver halide solution in the prior art is generally about 10% at most); the solution can be regenerated in precipitating agent such as water and alcohol. The preparation method of the high-concentration silver halide solution and the regeneration method of the silver halide have simple processes, high efficiency and environmental protection.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

The mass concentrations mentioned in the following examples and comparative examples are equivalent mass concentrations of silver halide.