CN111621654A - Rhenium-removing trapping agent and preparation method thereof - Google Patents

Rhenium-removing trapping agent and preparation method thereof Download PDF

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CN111621654A
CN111621654A CN202010386682.XA CN202010386682A CN111621654A CN 111621654 A CN111621654 A CN 111621654A CN 202010386682 A CN202010386682 A CN 202010386682A CN 111621654 A CN111621654 A CN 111621654A
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rhenium
ethanol
capture agent
evaporation
product
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CN111621654B (en
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陈振岩
房大维
王雷
曹民强
肖程
李岩
满安静
熊耀华
李清春
颜强
洪波
孙建华
刘日强
孙平
邵建欣
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China National Petroleum Corp
Liaohe Petroleum Exploration Bureau
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China National Petroleum Corp
Liaohe Petroleum Exploration Bureau
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a rhenium-removing trapping agent and a preparation method thereof. The preparation method of the rhenium-removing capture agent comprises the following steps: the method comprises the following steps: mixing tertiary amine, mixed solution of ethanol and dichloromethane and hydrochloric acid for reaction, and evaporating to obtain the product containing [ R3NH][Cl]The evaporation product of (4); step two: and mixing the evaporation product with a proper amount of ethanol to obtain the rhenium-removing capture agent. The invention also provides a rhenium-removing capture agent prepared by the method. The rhenium-removing capture agent has the advantages of simple preparation, easy large-scale production and high elution efficiency, the elution rate is up to more than 98 percent, the product purity is up to 99.9 percent, and the rhenium-removing capture agent has good industrial application value.

Description

Rhenium-removing trapping agent and preparation method thereof
Technical Field
The invention relates to a rhenium-removing trapping agent and a preparation method thereof, belonging to the technical field of wet metallurgy.
Background
Rhenium (Re) belongs to a rare metal, has extremely low content in nature, and has no single natural mineral with rhenium at present, which is mainly associated with molybdenite and bornite. Rhenium has unique and excellent physical and chemical properties such as high melting point, high boiling point, large density, excellent ductility, formability, catalytic activity and the like, so that rhenium and the rhenium alloy have huge application prospects in the fields of petrochemical industry, aerospace, metallurgy, national defense and the like, and are in short supply and demand in the market. Common methods for separating and enriching rhenium include a solvent extraction separation method, an ion exchange method, a liquid membrane method, an oxidation-reduction method, a precipitation separation method and an activated carbon adsorption method.
According to research, abundant rhenium resources are associated in partially leachable uranium deposit in China, and when the associated uranium resources are subjected to in-situ leaching mining, rhenium can be well leached into solution by adopting either acid leaching or alkali leaching. Due to the low rhenium content, the ion exchange method is mostly used for recovering trace rhenium in the immersion liquid. The reports on strongly basic anion resin and weakly basic anion resin for recovering rhenium by using ion exchange resin are provided. Strong alkali anion exchange resin has strong adsorption selectivity to rhenium ion, but HClO is used4、HNO3Or NH4The SCN solution elutes rhenium from the resin due to the introduction of ClO4 -、NO3 -Impurity ions are generated, so that high-purity ammonium perrhenate is difficult to prepare; the weak-base anion exchange resin has low adsorption selectivity to rhenium and almost has no effect on the adsorption of trace rhenium. Due to the low rhenium concentration in the leaching solution (<1.0mg/L), most of which adopt basic anion exchange resin or other functional resin, but the resin has no effective method for eluting rhenium, so that low-concentration rhenium in uranium mine partially soaked in China can not be effectively recovered, and rhenium resource is greatly wasted. Therefore, the development and design of a rhenium-removing capture agent are urgently needed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a rhenium-removing capture agent and a preparation method thereof. The rhenium-removing capture agent has the advantages of simple preparation, easy large-scale production and high elution efficiency.
In order to achieve the aim, the invention provides a preparation method of a rhenium-removing capture agent, which comprises the following steps:
the method comprises the following steps: mixing tertiary amine, mixed solution of ethanol and dichloromethane and hydrochloric acid for reaction, and evaporating to obtain the product containing [ R3NH][Cl]The evaporation product of (4);
step two: and mixing the evaporation product with a proper amount of ethanol to obtain the rhenium-removing capture agent.
According to the specific embodiment of the invention, the mass ratio of the mixed solution of the tertiary amine, the ethanol and the dichloromethane and the hydrochloric acid can be controlled to be 1-10:5-20: 2-20.
According to an embodiment of the present invention, in the mixed solution of ethanol and dichloromethane, the volume ratio of ethanol to dichloromethane may be controlled to be 2: 1.
According to a particular embodiment of the invention, the evaporation product contains [ R ]3NH][Cl]Wherein R represents an alkyl chain in a tertiary amine, i.e. formula R of a tertiary amine3N。
According to a specific embodiment of the present invention, the tertiary amine used may be one or a combination of two or more of Trioctylamine (TOA), Triisooctylamine (TiOA), and trioctydecylalkyl tertiary amine (N235). The structures of trioctylamine, triisooctylamine, and trioctydecylalkyl tertiary amine are shown below. In the structures of the compounds, N is respectively connected with three branched chains, and the structures of the three branched chains are the same, except that the branched chain connected with the trioctyl decyl tertiary amine has eight to ten carbons, and the branched chains of the trioctyl amine and the triisooctylamine have eight carbons, but the structures of the three branched chains are similar, and the three branched chains have stronger ion association capacity because of the structure, so that the formed [ R3NH][Cl]Rhenium can be eluted efficiently.
Figure BDA0002484268510000021
According to an embodiment of the present invention, in step two, the amount of ethanol may be controlled to be [ R ] in the evaporation product3NH][Cl]5-20 times of the mass of (A).
According to a specific embodiment of the present invention, in the step one, the temperature of the reaction may be controlled to be 25 to 35 ℃ and the time may be 5 to 12 hours.
According to a specific embodiment of the present invention, in the first step, the temperature of evaporation may be controlled to be 5 to 10 ℃ higher than the boiling point of the solvent. When the solvent is a mixed solvent, the boiling point of the solvent is selected from the boiling point temperature of the solvent with the highest boiling point.
According to a specific embodiment of the present invention, in the first step, the evaporation can be performed by means of rotary evaporation, preferably at a rotation speed of 20-50 r/min.
According to a particular embodiment of the invention, the preparation process may comprise the following particular steps:
the method comprises the following steps: adding mixed solution of tertiary amine, ethanol and dichloromethane and hydrochloric acid into a reaction kettle, stirring and refluxing at 25-35 deg.C for 5-12h, and evaporating to obtain a product containing [ R3NH][Cl]Evaporation product of (1) (viscous liquid);
step two: adding [ R ] in the evaporation product to the evaporation product3NH][Cl]5-20 times of ethanol to obtain the rhenium-removing capture agent.
The invention also provides a rhenium-removing capture agent which is prepared by the method.
Against the difficulty of rhenium elution of anion exchange resins, or with HClO4、HNO3Or NH4The SCN solution elutes rhenium from the resin due to the introduction of ClO4 -、NO3 -The invention provides a rhenium removal trapping agent and a preparation method thereof, and solves the problem that high-purity ammonium perrhenate is difficult to prepare by impurity ions. The rhenium-removing capture agent has the advantages of simple preparation, easy large-scale production and high elution efficiency, the elution rate is up to more than 98 percent, the product purity is up to 99.9 percent, and the rhenium-removing capture agent has good industrial application value.
Drawings
FIG. 1 is a nuclear magnetic spectrum of [ TOAH ] [ Cl ] prepared in example 2.
FIG. 2 is a nuclear magnetic spectrum of [ TiOAH ] [ Cl ] prepared in example 3.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides a rhenium removal capture agent, which is prepared by the following method:
adding 4 parts of N235, 12 parts of mixed solution of ethanol and dichloromethane into a reaction kettle, adding 6 parts of hydrochloric acid, stirring and refluxing at 25-35 ℃ for reaction for 7 hours, and then performing rotary evaporation to remove redundant organic solvent to obtain viscous liquid [ N235H ] [ Cl ];
according to the amount of [ N235H ] [ Cl ], 15 times of ethanol is added by mass to obtain the rhenium removal capture agent.
And (3) capture performance testing:
adding a rhenium removal capture agent with the volume 3 times that of the resin into the resin with adsorption equilibrium, collecting the rhenium removal capture agent passing through the column, then adding ammonia water with the same volume, stirring and contacting for 20min, standing and layering, collecting a water phase 3L, wherein the rhenium content before elution is 67.85g, and the rhenium content of the water phase is 22.23g/L, so that the elution rate is 98.29%; elution rate-total mass of rhenium in the aqueous phase/total mass of rhenium in the resin before elution;
and then, obtaining ammonium rhenate through the steps of evaporation, recrystallization and the like, wherein the purity of the ammonium rhenate is 99.92%.
Example 2
This example provides a rhenium removal capture agent, which is prepared by the following method:
adding 6 parts of TOA, 14 parts of mixed solution of ethanol and dichloromethane into a reaction kettle, adding 8 parts of hydrochloric acid, stirring and refluxing at 25-35 ℃ for 8 hours, and then performing rotary evaporation to remove redundant organic solvent to obtain viscous liquid [ TOAH ] [ Cl ], wherein the nuclear magnetic spectrum of the liquid is shown in figure 1;
according to the amount of [ TOAH ] [ Cl ], 17 times of ethanol is added by mass to obtain the rhenium-removing capture agent.
And (3) capture performance testing:
adding a rhenium removal capture agent with the volume 3 times that of the resin into the resin with adsorption equilibrium, collecting the rhenium removal capture agent passing through the column, then adding ammonia water with the same volume, stirring and contacting for 20min, standing and layering, collecting a water phase 3L, wherein the rhenium content before elution is 68.37g, and the rhenium content of the water phase is 22.39g/L, so that the elution rate is 98.24%;
then, the ammonium rhenate is obtained through the steps of evaporation, recrystallization and the like, and the purity of the ammonium rhenate is 99.94%.
Example 3
This example provides a rhenium removal capture agent, which is prepared by the following method:
adding 2 parts of TiOA, 8 parts of mixed solution of ethanol and dichloromethane into a reaction kettle, adding 4 parts of hydrochloric acid, stirring and refluxing for reaction for 6 hours at 25-35 ℃, and then performing rotary evaporation to remove redundant organic solvent to obtain viscous liquid [ TiOAH ] [ Cl ], wherein the nuclear magnetic spectrum of the liquid is shown in figure 2;
according to the amount of [ TiOAH ] [ Cl ], adding 10 times of ethanol by mass to obtain the rhenium-removed capture agent.
And (3) capture performance testing:
adding a rhenium removal capture agent with the volume 3 times that of the resin into the resin with adsorption equilibrium, collecting the rhenium removal capture agent passing through the column, then adding ammonia water with the same volume, stirring and contacting for 20min, standing and layering, collecting a water phase 3L, wherein the rhenium content before elution is 67.55g, and the rhenium content of the water phase is 22.16g/L, so that the elution rate is 98.41%;
and then, obtaining ammonium rhenate through the steps of evaporation, recrystallization and the like, wherein the purity of the ammonium rhenate is 99.93%.

Claims (10)

1. A preparation method of a rhenium-removing capture agent comprises the following steps:
the method comprises the following steps: mixing tertiary amine, mixed solution of ethanol and dichloromethane and hydrochloric acid for reaction, and evaporating to obtain the product containing [ R3NH][Cl]The evaporation product of (4);
step two: and mixing the evaporation product with a proper amount of ethanol to obtain the rhenium-removing capture agent.
2. The preparation method according to claim 1, wherein the mass ratio of the mixed solution of the tertiary amine, ethanol and dichloromethane to the hydrochloric acid is 1-10:5-20: 2-20.
3. The production method according to claim 1 or 2, wherein the volume ratio of ethanol to dichloromethane in the mixed solution of ethanol and dichloromethane is 2: 1.
4. The production method according to any one of claims 1 to 3, wherein the tertiary amine is one or a combination of two or more of trioctylamine, triisooctylamine, and trioctydecylalkyl tertiary amine.
5. The production method according to any one of claims 1 to 4, wherein, in the second step, the ethanol is used in an amount of [ R ] in the evaporation product3NH][Cl]5-20 times of the mass of (A).
6. The process according to any one of claims 1 to 5, wherein in step one, the reaction is carried out at a temperature of 25 to 35 ℃ for a period of 5 to 12 hours.
7. The production method according to any one of claims 1 to 6, wherein the temperature of the evaporation is 5 to 10 ℃ higher than the boiling point of the solvent.
8. The method according to any one of claims 1 to 7, wherein the evaporation is carried out by means of rotary evaporation, preferably at a speed of 20 to 50 r/min.
9. The method according to any one of claims 1 to 8, wherein the method comprises the following specific steps:
the method comprises the following steps: adding mixed solution of tertiary amine, ethanol and dichloromethane and hydrochloric acid into a reaction kettle, stirring and refluxing at 25-35 deg.C for 5-12h, and evaporating to obtain a product containing [ R3NH][Cl]The evaporation product of (4);
step two: adding [ R ] in the evaporation product to the evaporation product3NH][Cl]5-20 times of ethanol to obtain the rhenium-removing capture agent.
10. A de-rhenium capture agent prepared by the method of any one of claims 1 to 9.
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Citations (5)

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Publication number Priority date Publication date Assignee Title
CN101514165A (en) * 2009-03-24 2009-08-26 中国科学院长春应用化学研究所 Method for preparing liquid containing metallic ions by employing extraction reaction
CN103073499A (en) * 2012-11-30 2013-05-01 辽宁大学 Method for preparing rhenium ion liquid by extraction method
WO2014158043A1 (en) * 2013-03-26 2014-10-02 Закрытое Акционерное Общество Торговый Дом "Галион" Method for recovery of rhenium from nickel-containing superalloys
CN107519948A (en) * 2017-08-09 2017-12-29 中国地质科学院郑州矿产综合利用研究所 Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate
CN108300858A (en) * 2018-04-03 2018-07-20 金川集团股份有限公司 A method of extracting high-purity rehenic acid ammonium from rhenium-containing extract liquor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101514165A (en) * 2009-03-24 2009-08-26 中国科学院长春应用化学研究所 Method for preparing liquid containing metallic ions by employing extraction reaction
CN103073499A (en) * 2012-11-30 2013-05-01 辽宁大学 Method for preparing rhenium ion liquid by extraction method
WO2014158043A1 (en) * 2013-03-26 2014-10-02 Закрытое Акционерное Общество Торговый Дом "Галион" Method for recovery of rhenium from nickel-containing superalloys
CN107519948A (en) * 2017-08-09 2017-12-29 中国地质科学院郑州矿产综合利用研究所 Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate
CN108300858A (en) * 2018-04-03 2018-07-20 金川集团股份有限公司 A method of extracting high-purity rehenic acid ammonium from rhenium-containing extract liquor

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