阅读说明：本技术 一种贵金属铑回收过程除铁的方法 (Method for removing iron in precious metal rhodium recovery process ) 是由 谭学苓 郭喜文 谭承刚 蒋巨光 张照飞 于 2019-09-29 设计创作，主要内容包括：本发明公开了一种贵金属铑回收过程除铁的方法,包括如下步骤：将回收的三苯基膦乙酰丙酮羰基铑催化剂废弃溶液浓缩、焚烧,得混合物；将混合物氯化,得到氯化铑和氯化铁的混合物；向氯化铑和氯化铁的混合物中加入氯盐和盐酸溶液,反应后蒸干,制得氯铑酸盐和氯化铁的混合物；用极性有机溶剂对氯铑酸盐和氯化铁的混合物进行洗涤,除去氯化铁；将剩余的氯铑酸盐制成金属铑或氯化铑。三苯基膦乙酰丙酮羰基铑催化剂废弃溶液经浓缩焚烧后,得到固体铑和铁氧化混合物。(The invention discloses a method for removing iron in a precious metal rhodium recovery process, which comprises the following steps: concentrating and incinerating the recovered triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution to obtain a mixture; chlorinating the mixture to obtain a mixture of rhodium chloride and ferric chloride; adding chloride and hydrochloric acid solution into a mixture of rhodium chloride and ferric chloride, reacting, and evaporating to dryness to prepare a mixture of chlororhodate and ferric chloride; washing the mixture of chlororhodate and ferric chloride with a polar organic solvent to remove ferric chloride; the remaining chlororhodate is made into metal rhodium or rhodium chloride. After the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution is concentrated and burned, a solid rhodium and iron oxide mixture is obtained.)

1. A method for removing iron in the recovery process of noble metal rhodium is characterized by comprising the following steps: the method comprises the following steps:

concentrating and incinerating the recovered triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution to obtain a mixture;

chlorinating the mixture to obtain a mixture of rhodium chloride and ferric chloride;

adding chloride and hydrochloric acid solution into a mixture of rhodium chloride and ferric chloride, reacting, and evaporating to dryness to prepare a mixture of chlororhodate and ferric chloride;

washing the mixture of chlororhodate and ferric chloride with a polar organic solvent to remove ferric chloride;

the remaining chlororhodate is made into metal rhodium or rhodium chloride.

After the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution is concentrated and burned, a solid rhodium and iron oxide mixture is obtained.

2. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the mass fraction of the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution after concentration is 0.5-1%.

3. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the mixture was chlorinated with chlorine at a temperature of 350-.

4. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the chlorine salt is sodium chloride or potassium chloride.

5. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: dissolving a mixture of rhodium chloride and ferric chloride in a 0.8-1.2% hydrochloric acid solution, and adding sodium chloride according to the molar ratio of the rhodium chloride to the sodium chloride of 1: 5.5-6.5.

6. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the sodium chloride is of analytical grade.

7. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the polar organic solvent is absolute ethyl alcohol, acetone or methanol.

8. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: washing the mixture of chlororhodate and ferric chloride with a polar organic solvent at 30-50 deg.C for 1-1.5 h;

further, the number of washing is 2 to 4.

9. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the method for preparing metal rhodium by chlororhodate comprises the following steps: hydrogen is adopted to reduce chlororhodanate to prepare metal rhodium, and the reaction temperature is 580-620 ℃.

10. The method for removing iron in the recovery process of noble metal rhodium according to claim 1, which is characterized in that: the method for preparing rhodium chloride from chlororhodate comprises the following steps: dissolving chlororhodate in deionized water, adding sodium hydroxide to prepare rhodium hydroxide, and adding hydrochloric acid to the rhodium hydroxide to prepare rhodium chloride.

Technical Field

The invention relates to a method for removing iron in a recovery process of noble metal rhodium, which is suitable for a purification process of a noble metal rhodium compound, is particularly suitable for removing iron ions in a recovery process of a waste acetylacetonatocarbonylrhodium catalyst, and has higher application value in the aspect of removing iron from the rhodium compound.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

At present, the industrial production of butanol and octanol generally adopts propylene hydroformylation to synthesize butyraldehyde and further synthesize the butanol and octanol. The triphenylphosphine acetylacetonatocarbonylrhodium catalyst is the core of the production process. The catalyst contains noble metal rhodium, so that the noble metal rhodium has high value in recovery after the catalyst is out of service. However, in the using process of the catalyst, because of factors such as corrosion of equipment pipelines, entrainment of raw materials and the like, part of iron ions are inevitably carried in, so that the problem of recovery and purification of the noble metal rhodium is caused. At present, in China, a resin adsorption method is generally adopted in a rhodium compound iron removal process, but the resin has certain adsorption capacity on rhodium compounds, so that the recovery rate of noble metal rhodium is reduced, and meanwhile, the repeated adsorption and desorption process of the resin is complex, and a large amount of waste acid and waste water are also generated.

Disclosure of Invention

In order to solve the technical problems in the prior art, the invention aims to provide a method for removing iron in the recovery process of noble metal rhodium, which has the advantages of simple process, high recovery rate of noble metal rhodium, high purity and no generation of more waste acid and waste water.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method for removing iron in a precious metal rhodium recovery process comprises the following steps:

concentrating and incinerating the recovered triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution to obtain a mixture;

chlorinating the mixture to obtain a mixture of rhodium chloride and ferric chloride;

adding chloride and hydrochloric acid solution into a mixture of rhodium chloride and ferric chloride, reacting, and evaporating to dryness to prepare a mixture of chlororhodate and ferric chloride;

washing the mixture of chlororhodate and ferric chloride with a polar organic solvent to remove ferric chloride;

the remaining chlororhodate is made into metal rhodium or rhodium chloride.

After the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution is concentrated and burned, a solid rhodium and iron oxide mixture is obtained.

In some embodiments, the triphenylphosphine acetylacetonatocarbonylrhodium catalyst waste solution has a mass fraction after concentration of 0.5% to 1%.

In some embodiments, the mixture is chlorinated with chlorine gas at a temperature of 350-.

In some embodiments, the chloride salt is sodium chloride or potassium chloride.

Further, a mixture of rhodium chloride and ferric chloride is dissolved in a 0.8-1.2% hydrochloric acid solution, and sodium chloride is added according to the molar ratio of the rhodium chloride to the sodium chloride of 1: 5.5-6.5.

Further, the sodium chloride is of analytical grade. To avoid further entrainment of transition metal impurity ions.

In some embodiments, the polar organic solvent is absolute ethanol, acetone, or methanol. Washing with nonpolar organic solvent such as anhydrous ethanol and acetone, wherein ferric chloride is easily soluble in ethanol, and sodium chlororhodate is basically insoluble in ethanol. Ferric chloride carried by the washed absolute ethyl alcohol is dissolved in the ethyl alcohol, so that the separation of the ferric chloride and the chlororhodate is realized.

In some embodiments, the mixture of chlororhodate and ferric chloride is washed with the polar organic solvent at a temperature of from 30 to 50 ℃ (in this temperature interval, ferric chloride has high solubility in the solvent, and at too high a temperature, the solvent approaches the boiling point, resulting in substantial evaporation of the solvent), and the washing time is from 1 to 1.5 hours.

Further, the number of washing is 2 to 4. The ferric chloride can be removed more thoroughly by washing for many times, and the purity of the chlororhodate is improved.

In some embodiments, the method of making rhodium metal from chlororhodate is: hydrogen is adopted to reduce chlororhodanate to prepare metal rhodium, and the reaction temperature is 580-620 ℃.

In some embodiments, the method of making rhodium chloride from chlororhodate is: dissolving chlororhodate in deionized water, adding sodium hydroxide to prepare rhodium hydroxide, and adding hydrochloric acid to the rhodium hydroxide to prepare rhodium chloride.

The invention has the beneficial effects that:

the method has simple process, high recovery rate of the noble metal rhodium and high purity because the iron is washed and removed in the rhodium recovery process, and simultaneously, waste acid and waste water can not be generated.

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, 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 invention belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.