Method for extracting rhenium from rhenium-containing waste organic phase
The new extraction process addresses the challenge of recovering rhenium from rhenium-containing waste organic phases by using reverse extraction and solvent techniques, achieving a high rhenium recovery rate and effective separation from impurities, resulting in high-purity rhenium oxide production.
Patent Information
- Application Number
- CN202411781577.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-05
- Publication Date
- 2025-03-14
AI Technical Summary
The existing methods for recovering rhenium (Re) from rhenium-containing waste organic phases face challenges due to the difficulty in separating rhenium from impurities like Bi and Sb, leading to low rhenium recovery rates and inefficient processing of rhenium-containing waste organic phases, which are often discarded as waste oil.
A new extraction process involving reverse extraction with alkaline solutions, followed by acidification, solvent extraction, washing, and recrystallization to produce high-purity rhenium oxide, utilizing specific ratios of reagents and conditions to achieve effective separation and recovery of rhenium from rhenium-containing waste organic phases.
This process achieves a rhenium recovery rate of ≥95% and effectively separates rhenium from impurities, enabling the production of high-purity rhenium oxide products with improved resource utilization.
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Figure CN119614911A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of nonferrous metal metallurgy, and in particular relates to a method for extracting rhenium from a waste organic phase containing rhenium. Background Art
[0002] Rhenium is a rare metal with a content of about 10 -7 %, mostly associated with minerals such as molybdenum, copper, lead, zinc, platinum, tantalum, niobium, and rare earths, and it is difficult to be recycled alone. The economically valuable raw materials for rhenium extraction are molybdenite and copper concentrate. The global production of rhenium mainly depends on the enrichment and recovery of porphyry copper mines in the process of copper and molybdenum recovery. At present, the commonly used rhenium recovery methods in industry are mainly chemical precipitation, ion exchange and extraction-crystallization.
[0003] The rhenium-containing raw materials are subjected to organic phase extraction, washing, stripping and other processes to recover the valuable metal rhenium. Due to the influence of factors such as impurities or suspended fine particles in the raw materials, it will lead to: ① the formation of a third phase in the extraction process; ② hydrolysis of impurities in the washing process; ③ hydrolysis of impurities in the stripping process. All of the above will lead to the destruction of the organic phase and the formation of a waste organic phase containing rhenium. Most rhenium extraction production companies will produce waste organic phase containing rhenium, which mainly contains rhenium and a small amount of Sb and Bi impurity elements. Due to the difficulty of stratification and high impurities, it is treated as waste oil, which reduces the rhenium recovery rate and creates difficulties for the traditional rhenium extraction and recovery process. This type of waste organic phase containing rhenium must first solve the stratification problem, and then strip the rhenium in it into the liquid phase to further produce crude ammonium rhenate products.
[0004] How to solve the problem of difficulty in separating the organic phase containing rhenium and the separation of rhenium from bismuth and antimony impurities, realize the recovery of rhenium, and obtain high-grade crude ammonium rhenate products is a difficult problem both at home and abroad. For many years, various rhenium recovery manufacturers have been directly treating the organic phase containing rhenium as waste oil, resulting in rhenium loss and under-utilization of rhenium resources. This process can better realize the extraction and recovery of rhenium from the organic phase containing rhenium, and the process is simple and low-cost. Summary of the invention
[0005] The purpose of the present invention is to provide a new extraction process for extracting and recovering rhenium from waste organic phase containing rhenium, and converting it into 65% to 69% crude ammonium rhenate, which can be used as a raw material for purifying ammonium rhenate or producing high-purity rhenium.
[0006] In order to solve the above technical problems, the technical solution of the present invention is: a method for extracting rhenium from a waste organic phase containing rhenium, the method specifically comprising the following steps:
[0007] S1) stripping the waste organic phase containing rhenium, adding a certain amount of liquid alkali during the stripping process, heating to a certain temperature, and continuously stirring for a certain time, waiting; after the stripping is completed, standing for a certain time to obtain a rhenium-containing alkali solution and a waste organic phase after saponification;
[0008] S2) subjecting the rhenium-containing alkali solution obtained in S1) to an acidification process to obtain an acidified solution;
[0009] S3) adding an extraction agent to the acidified liquid obtained in S2) to extract to obtain a loaded organic phase;
[0010] S4) washing the loaded organic phase obtained in S3) with pure water to obtain a washed loaded organic phase;
[0011] S5) stripping the washed loaded organic phase obtained in S4) to obtain a rhenium-containing stripping solution;
[0012] S6) concentrating the rhenium-containing stripping solution obtained in S5) to obtain a concentrated solution, and then cooling and crystallizing the concentrated solution to obtain a crude ammonium rhenate product.
[0013] Furthermore, the rhenium-containing waste organic phase in S1) is an emulsified organic phase produced during the rhenium extraction process, and the rhenium content is 5 to 50 g / l.
[0014] Furthermore, in said S1), the heating temperature is 20-80°C, the stirring time is 2-12 hours, the standing time is 2-12 hours, and the alkalinity of the solution is controlled at 20-80 g / l.
[0015] Furthermore, in said S2), the acidity of the rhenium-containing alkali solution is controlled to be 50-200 g / l, the reaction time is 1-8 hours, and the reaction temperature is 10-60°C.
[0016] Furthermore, in said S3), the ratio of the extraction reagent to the acidified liquid is (2-80):1; and the extraction reagent is: kerosene, 2-octanol and trioctyl ammonium mixed in a ratio of 2:2:1.
[0017] Furthermore, the ratio of pure water to loaded organic phase in S4) is (4-20):1.
[0018] Furthermore, the stripping reagent in S5) is aqueous ammonia with a concentration of 5-20%; the ratio of aqueous ammonia to the organic phase after washing is (1-5):1.
[0019] Furthermore, the concentration specific gravity in said S6) is 1.01 to 1.25; and the cooling temperature is -20 to 5°C.
[0020] Furthermore, the rhenium recovery rate of the method is ≥95%.
[0021] A crude ammonium rhenate is prepared by the above method.
[0022] The beneficial effects of the present invention are as follows: the method utilizes liquid alkali to react with rhenium in the rhenium-containing waste organic phase to force rhenium to be stripped into the liquid phase, thereby directly separating rhenium from the impurities of antimony and bismuth. At the same time, the waste oil and the rhenium-containing alkali liquid are well separated after saponification, and the rhenium recovery rate reaches more than 95%. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 The present invention discloses a process flow of a method for extracting rhenium from a waste organic phase containing rhenium. DETAILED DESCRIPTION
[0024] The content of the present invention is further described below in conjunction with the process flow diagram and examples of the present invention.
[0025] like Figure 1 As shown, the present invention provides a method for extracting rhenium from a waste organic phase containing rhenium, and the method specifically comprises the following steps:
[0026] S1) stripping the waste organic phase containing rhenium, adding a certain amount of liquid alkali during the stripping process, heating to a certain temperature, and continuously stirring for a certain time, waiting; after the stripping is completed, standing for a certain time to obtain a rhenium-containing alkali solution and a waste organic phase after saponification;
[0027] The rhenium-containing waste organic phase is an emulsified organic phase produced during the rhenium extraction process, and the rhenium content is 5 to 50 g / l.
[0028] S2) subjecting the rhenium-containing alkali solution obtained in S1) to an acidification process to obtain an acidified solution;
[0029] S3) adding an extraction agent to the acidified liquid obtained in S2) to extract to obtain a loaded organic phase;
[0030] S4) washing the loaded organic phase obtained in S3) with pure water to obtain a washed loaded organic phase;
[0031] S5) stripping the washed loaded organic phase obtained in S4) to obtain a rhenium-containing stripping solution;
[0032] S6) concentrating the rhenium-containing stripping solution obtained in S5) to obtain a concentrated solution, and then cooling and crystallizing the concentrated solution to obtain a crude ammonium rhenate product.
[0033] In the S1), the heating temperature is 20-80° C., the stirring time is 2-12 hours, and the standing time is 2-12 hours, and the alkalinity of the solution is controlled at 20-80 g / l.
[0034] In the step S2), the acidity of the rhenium-containing alkali solution is controlled to be 50-200 g / l, the reaction time is 1-8 hours, and the reaction temperature is 10-60°C.
[0035] The ratio of the extraction reagent to the acidified liquid in S3) is (2-80):1; and the extraction reagent is a mixture of kerosene, 2-octanol and trioctyl ammonium in the ratio of 2:2:1.
[0036] The ratio of pure water to loaded organic phase in S4) is (4-20):1.
[0037] The stripping reagent in S5) is ammonia water with a concentration of 5-20%; the ratio of ammonia water to the organic phase after washing is (1-5):1.
[0038] The specific gravity of the concentrate in S6) is 1.01 to 1.25; the cooling temperature is -20 to 5°C.
[0039] The rhenium recovery rate of the method is ≥95%.
[0040] Embodiment 1:
[0041] The waste organic phase contains a small amount of impurities such as Bi and Sb. In the process of stripping rhenium from the waste organic phase containing rhenium, a certain amount of liquid alkali is added, the temperature is raised and stirred, the temperature is controlled at 20°C, and the stirring time is 2 hours. After the stripping is completed, it is allowed to stand for 2 hours, and the layers are separated to obtain rhenium-containing alkali solution and saponified waste oil. The rhenium-containing alkali solution is introduced into a 50g / l sulfuric acid solution in a certain proportion for acidification, stirring, and reacting at room temperature for 2 hours to obtain an acidified liquid. The acidified liquid is added with an extraction reagent for extraction, and the ratio of the extraction reagent to the acidified liquid is controlled to be 2:1 to obtain a loaded organic phase; the loaded organic phase is washed with pure water, and the ratio of pure water to the loaded organic phase is controlled to be 4:1 to obtain a washed loaded organic phase. The loaded organic phase after washing is stripped with (5-20)% ammonia water, and the ratio of ammonia water to the loaded organic phase after washing is controlled to be 1:1, so as to obtain a rhenium-containing stripping solution; the rhenium-containing stripping solution is concentrated, and the specific gravity is controlled to be 1.01, so as to obtain a concentrated liquid; the concentrated liquid is cooled and crystallized, and the cooling temperature is controlled to be -20°C, so as to obtain a crude ammonium rhenate product.
[0042] After the above steps, the rhenium recovery rate is ≥95%.
[0043] Example 2
[0044] The waste organic phase contains a small amount of impurities such as Bi and Sb. In the process of stripping rhenium from the waste organic phase containing rhenium, a certain amount of liquid alkali is added, the temperature is raised and stirred, the temperature is controlled at 80°C, and the stirring time is 12 hours. After the stripping is completed, it is allowed to stand for 12 hours and separated into layers to obtain rhenium-containing alkali solution and saponified waste oil. The rhenium-containing alkali solution is introduced into a 200g / l sulfuric acid solution in a certain proportion for acidification, stirring, and reacting at room temperature for 8 hours to obtain an acidified liquid; the acidified liquid is added with an extraction reagent for extraction, and the ratio of the extraction reagent to the acidified liquid is controlled to be 80:1 to obtain a loaded organic phase; the loaded organic phase is washed with pure water, and the ratio of pure water to the loaded organic phase is controlled to be 20:1 to obtain a washed loaded organic phase. The organic phase loaded after water washing is stripped with (5-20)% concentration of ammonia water, and the ratio of ammonia water to the organic phase loaded after water washing is controlled to be 5:1, so as to obtain a rhenium-containing stripping solution; the rhenium-containing stripping solution is concentrated, and the specific gravity is controlled to be 1.25 to obtain a concentrated liquid; the concentrated liquid is cooled and crystallized, and the cooling temperature is controlled to be 5°C to obtain a crude ammonium rhenate product.
[0045] After the above steps, the rhenium recovery rate is ≥95%.
[0046] Example 3
[0047] The waste organic phase contains a small amount of impurities such as Bi and Sb. In the process of stripping rhenium from the waste organic phase containing rhenium, a certain amount of liquid alkali is added, the temperature is raised and stirred, the temperature is controlled at 50°C, and the stirring time is 6 hours. After the stripping is completed, it is allowed to stand for 5 hours and separated into layers to obtain rhenium-containing alkali solution and saponified waste oil. The rhenium-containing alkali solution is introduced into a 90g / l sulfuric acid solution in a certain proportion for acidification, stirring, and reacting at room temperature for 6 hours to obtain an acidified liquid. The acidified liquid is extracted with an extraction reagent, and the ratio of the extraction reagent to the acidified liquid is controlled to be 50:1 to obtain a loaded organic phase; the loaded organic phase is washed with pure water, and the ratio of pure water to the loaded organic phase is controlled to be 10:1 to obtain a washed loaded organic phase. The organic phase loaded after water washing is stripped with ammonia water of a certain concentration, and the ratio of ammonia water to the organic phase loaded after water washing is controlled to be 3:1, so as to obtain a rhenium-containing stripping solution; the rhenium-containing stripping solution is concentrated, and the specific gravity is controlled to be 1.15 to obtain a concentrated liquid; the concentrated liquid is cooled and crystallized, and the cooling temperature is controlled to -10°C to obtain a crude ammonium rhenate product.
[0048] After the above steps, the rhenium recovery rate is ≥95%.
[0049] The above is a detailed introduction to a rare earth lubricated high-speed train brake pad and a preparation method provided in the embodiment of the present application. The description of the above embodiment is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as limiting the present application.
[0050] For example, certain words are used in the specification and claims to refer to specific components. Those skilled in the art should understand that hardware manufacturers may use different nouns to refer to the same component. This specification and claims do not use differences in names as a way to distinguish components, but use differences in the functions of components as the criteria for distinction. As mentioned throughout the specification and claims, "including" and "comprising" are open-ended terms, so they should be interpreted as "including / including but not limited to". "Approximately" means that within an acceptable error range, those skilled in the art can solve the technical problem within a certain error range and basically achieve the technical effect. The subsequent description of the specification is a preferred embodiment of the present application, but the description is for the purpose of illustrating the general principles of the present application, and is not used to limit the scope of the present application. The scope of protection of the present application shall be determined by the definition of the attached claims.
[0051] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a product or system including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such a product or system. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the product or system including the elements.
[0052] It should be understood that the term "and / or" used in this article is only a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.
[0053] The above description shows and describes several preferred embodiments of the present application, but as mentioned above, it should be understood that the present application is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the application concept described herein through the above teachings or the technology or knowledge of the relevant field. The changes and modifications made by those skilled in the art do not deviate from the spirit and scope of the present application, and should be within the scope of protection of the claims attached to the present application.
Claims
1. A method for extracting rhenium from a waste organic phase containing rhenium, characterized in that: The method specifically comprises the following steps: S1) stripping the waste organic phase containing rhenium, adding a certain amount of liquid alkali during the stripping process, heating to a certain temperature, and continuously stirring for a certain time, waiting; after the stripping is completed, standing for a certain time to obtain a rhenium-containing alkali solution and a waste organic phase after saponification; S2) subjecting the rhenium-containing alkali solution obtained in S1) to an acidification process to obtain an acidified solution; S3) adding an extraction agent to the acidified liquid obtained in S2) to extract to obtain a loaded organic phase; S4) washing the loaded organic phase obtained in S3) with pure water to obtain a washed loaded organic phase; S5) stripping the washed loaded organic phase obtained in S4) to obtain a rhenium-containing stripping solution; S6) concentrating the rhenium-containing stripping solution obtained in S5) to obtain a concentrated solution, and then cooling and crystallizing the concentrated solution to obtain a crude ammonium rhenate product.
2. The method according to claim 1, characterized in that The rhenium-containing waste organic phase in S1) is an emulsified organic phase produced during the rhenium extraction process, and the rhenium content is 5 to 50 g / l.
3. The method according to claim 1, characterized in that In the S1), the heating temperature is 20-80° C., the stirring time is 2-12 hours, and the standing time is 2-12 hours, and the alkalinity of the solution is controlled at 20-80 g / l.
4. The method according to claim 1, characterized in that: In the step S2), the acidity of the rhenium-containing alkali solution is controlled to be 50-200 g / l, the reaction time is 1-8 hours, and the reaction temperature is 10-60°C.
5. The method according to claim 1, characterized in that The ratio of the extraction reagent to the acidified liquid in S3) is (2-80):1; and the extraction reagent is a mixture of kerosene, 2-octanol and trioctyl ammonium in the ratio of 2:2:
1.
6. The method according to claim 1, characterized in that The ratio of pure water to loaded organic phase in S4) is (4-20):
1.
7. The method according to claim 1, characterized in that The stripping reagent in S5) is ammonia water with a concentration of 5-20%; the ratio of ammonia water to the organic phase after washing is (1-5):
1.
8. The method according to claim 1, characterized in that The specific gravity of the concentrate in S6) is 1.01 to 1.25; the cooling temperature is -20 to 5°C.
9. The method according to claim 1, characterized in that: The rhenium recovery rate of the method is ≥95%.
10. A crude ammonium rhenate, characterized in that: The crude ammonium rhenate is prepared by the method according to any one of claims 1 to 9.