阅读说明：本技术 一种含碘化亚铜混合物料回收硫酸铜、碘的方法 (Method for recovering copper sulfate and iodine from cuprous iodide-containing mixed material ) 是由 于国清 刘会军 朱振宗 周丽娜 郭平 董林峰 于 2020-04-08 设计创作，主要内容包括：本发明属于回收硫酸铜、碘领域,具体公开了一种含碘化亚铜混合物料回收硫酸铜、碘的方法,本发明通过在热稀硫酸中加双氧水,能够同时氧化碘与铜,通过空气吹碘,得到高含量碘单质,母液过滤得到较纯的硫酸铜溶液,步骤简单,减少中间过程损耗,收率高。本发明工艺简单、易于操作、回收率高的含铜废料回收硫酸铜、碘的方法,碘收率达到99％以上,硫酸铜收率99％以上,本工艺安全环保,设备要求低,硫酸铜、碘回收率高,易于产业化。(The invention belongs to the field of copper sulfate and iodine recovery, and particularly discloses a method for recovering copper sulfate and iodine from a cuprous iodide-containing mixed material. The method for recovering the copper sulfate and the iodine from the copper-containing waste material has the advantages of simple process, easy operation and high recovery rate, the iodine yield reaches more than 99 percent, the copper sulfate yield is more than 99 percent, the process is safe and environment-friendly, the equipment requirement is low, the recovery rate of the copper sulfate and the iodine is high, and the industrialization is easy.)

1. A method for recovering copper sulfate and iodine from a cuprous iodide-containing mixed material is characterized by comprising the following steps of:

1) adding sulfuric acid into the copper-containing waste, heating to reflux, and carrying out reflux heat preservation for 1 h;

2) dropwise adding hydrogen peroxide until iodine vapor appears;

3) performing water vapor distillation, dropwise adding hydrogen peroxide until no iodine vapor is evaporated, recovering iodine vapor to obtain iodine solution, and filtering the iodine solution to obtain iodine;

4) diluting the reaction liquid in the water vapor distillation reaction with water, heating up, and then carrying out hot filtration on the reaction liquid at 80 ℃ after heating up to 80 ℃ to obtain a copper sulfate solution.

2. The method for recovering the copper sulfate and the iodine from the cuprous iodide containing mixture as claimed in claim 1, wherein the mass concentration of the sulfuric acid in the step 1) is 30%.

3. The method for recovering the copper sulfate and the iodine from the cuprous iodide containing mixed material as claimed in claim 1, wherein the mass ratio of the sulfuric acid to the copper-containing waste in the step 1) is 2: 1.

4. The method for recycling copper sulfate and iodine by using the cuprous iodide mixed material as claimed in claim 1, wherein in step 2) and step 3), the mass concentration of hydrogen peroxide is the same and is 10%.

5. The method for recovering the copper sulfate and the iodine from the cuprous iodide containing mixed material as claimed in claim 1, wherein in the step 4), the amount of water added is 2 times of the mass of the cuprous iodide.

Technical Field

The invention belongs to the field of copper sulfate and iodine recovery, and particularly relates to a method for recovering copper sulfate and iodine from a cuprous iodide-containing mixed material.

Background

In the process of preparing the iodotrimethylsilane, copper powder is required to be added as an iodine protective agent, a large amount of copper-containing waste materials (cuprous iodide, copper oxide and the like) are generated, the copper-containing waste materials are mixed and cannot be directly recycled, and therefore, the iodine and the copper need to be separated and recycled. The traditional process for recovering copper sulfate and iodine comprises the following steps: crushing the copper-containing waste, adding the crushed copper-containing waste into a sodium hydroxide solution, heating to reflux, carrying out alkali boiling for 2 hours, cooling to room temperature, filtering, acidifying the filtrate, carrying out oxidation to recover iodine, adding 30% sulfuric acid into the filter cake, heating to reflux, carrying out acid boiling and refluxing for 2 hours, cooling, filtering, and recovering a copper sulfate solution. However, the prior art for recovering copper-containing materials has the defects that the steps for respectively recovering iodine and copper sulfate are complicated, the heating time is long, the energy consumption is high, and the 30 percent sulfuric acid cannot react with a copper simple substance in acid boiling, so that the copper recovery is incomplete.

Disclosure of Invention

The method for recovering the copper sulfate and the iodine from the cuprous iodide-containing mixed material has the advantages of high iodine and copper sulfate yield, safety, environmental protection, low equipment requirement, high copper sulfate and iodine recovery rate and easy industrialization.

The technical scheme of the invention is realized as follows:

a method for recovering copper sulfate and iodine from a cuprous iodide-containing mixed material comprises the following steps:

1) adding sulfuric acid into the copper-containing waste, heating to reflux, and carrying out reflux heat preservation for 1 h;

2) dropwise adding hydrogen peroxide until iodine vapor appears;

3) performing water vapor distillation, dropwise adding hydrogen peroxide until no iodine vapor is evaporated, recovering iodine vapor to obtain iodine solution, and filtering the iodine solution to obtain iodine;

4) diluting the reaction liquid in the water vapor distillation reaction with water, heating up, and then carrying out hot filtration on the reaction liquid at 80 ℃ after heating up to 80 ℃ to obtain a copper sulfate solution.

Further, in step 1), the mass concentration of sulfuric acid is 30%.

Further, in the step 1), the mass ratio of the sulfuric acid to the copper-containing waste is 2: 1.

Further, in the step 2) and the step 3), the mass concentration of hydrogen peroxide is the same and is 10%.

Further, in step 4), the amount of water added is 2 times the mass of the copper-containing waste.

The invention provides a method for recovering copper sulfate and iodine from a cuprous iodide-containing mixed material, which has the following advantages:

1) according to the invention, the iodine and the copper can be simultaneously oxidized by adding the hydrogen peroxide into the hot dilute sulfuric acid, the iodine with high content is obtained by blowing the iodine with air, the mother liquor is filtered to obtain a purer copper sulfate solution, the steps are simple, the loss in the middle process is reduced, and the yield is high.

2) The method for recovering the copper sulfate and the iodine from the copper-containing waste material has the advantages of simple process, easy operation and high recovery rate, the iodine yield reaches more than 99 percent, the copper sulfate yield is more than 99 percent, the process is safe and environment-friendly, the equipment requirement is low, the recovery rate of the copper sulfate and the iodine is high, and the industrialization is easy.

Drawings

FIG. 1 is a process flow diagram of the method for recovering copper sulfate and iodine from a cuprous iodide-containing mixture of the present invention;

FIG. 2 is a process flow diagram of a process for recovering iodine from a cuprous iodide-containing mixture of comparative example 1;

FIG. 3 is a process flow diagram of the method for recovering copper sulfate from cuprous iodide-containing mixed material of comparative example 1.

Detailed Description

Referring to the attached figure 1, the method for recovering copper sulfate and iodine from the cuprous iodide-containing mixed material, provided by the invention, comprises the following steps of:

1) adding sulfuric acid into the copper-containing waste, heating to reflux, and carrying out reflux heat preservation for 1 h;

2) dropwise adding hydrogen peroxide until iodine vapor appears;

3) performing water vapor distillation, dropwise adding hydrogen peroxide until no iodine vapor is evaporated, recovering iodine vapor to obtain iodine solution, and filtering the iodine solution to obtain iodine;

4) diluting the reaction liquid in the water vapor distillation reaction with water, heating up, and then carrying out hot filtration on the reaction liquid at 80 ℃ after heating up to 80 ℃ to obtain a copper sulfate solution.

Adding sulfuric acid into the copper-containing waste, heating to reflux, and carrying out reflux heat preservation for 1 h. As mentioned above, under hot sulphuric acid, cuprous iodide in the copper-containing waste can dissolve in the hot sulphuric acid. The mass concentration of the sulfuric acid is 30%; the mass ratio of the sulfuric acid to the copper-containing waste is 2: 1.

Then adding hydrogen peroxide dropwise until iodine vapor appears; the hydrogen peroxide is dropwise added into the cuprous iodide solution, so that the effect of oxidation can be achieved, and cuprous iodide is oxidized.

Distilling with water vapor, adding hydrogen peroxide dropwise until no iodine vapor is evaporated, recovering iodine vapor to obtain iodine solution, and filtering to obtain iodine; distilling the above water vapor, adding dropwise hydrogen peroxide for oxidation to generate iodine vapor, collecting iodine vapor to obtain iodine solution, and filtering to obtain iodine.

It should be noted that the concentrations of the hydrogen peroxide added twice are the same, and the mass concentration is 10%.

After no iodine vapor is discharged, adding water to the reaction liquid in the water vapor distillation reaction for dilution, heating to 80 ℃, and then carrying out heat filtration on the reaction liquid at 80 ℃ to obtain a copper sulfate solution. The amount of water added is 2 times the mass of cuprous iodide.

In order to further illustrate the present invention, the method for recovering copper sulfate and iodine by using cuprous iodide mixed material provided by the present invention is described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.