CN111218562A - Preparation of high-molecular extracting agent and method for efficiently recovering palladium by using high-molecular extracting agent - Google Patents
Preparation of high-molecular extracting agent and method for efficiently recovering palladium by using high-molecular extracting agent Download PDFInfo
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- CN111218562A CN111218562A CN202010025775.XA CN202010025775A CN111218562A CN 111218562 A CN111218562 A CN 111218562A CN 202010025775 A CN202010025775 A CN 202010025775A CN 111218562 A CN111218562 A CN 111218562A
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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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
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/34—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing sulfur, e.g. sulfonium
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- 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 discloses preparation of a high-molecular extraction component and a method for efficiently recovering palladium by using the high-molecular extraction component. The disclosed extraction composition simplifies the conventional multi-step process for such extraction by providing an extraction process that uses a single solvent extraction reagent to enable efficient recovery of palladium from base metal-containing hydrochloric acid media. The method for extracting and recovering palladium comprises the steps of preparing an acidic aqueous phase containing palladium and an organic phase containing extraction components, contacting the acid solution with a proper amount of the extracting agent for a sufficient time to form a palladium-containing supported organic matter, and washing and stripping palladium by using an acidified thiourea solution, thereby realizing the recovery of palladium.
Description
Technical Field
The invention belongs to the technical field of resource utilization and environmental protection, and particularly relates to a preparation method of a high-molecular extracting agent for extracting palladium ions and a recovery method for extracting the palladium ions by using the polymer.
Background
Palladium is widely used in high-tech fields such as industrial catalysis, aerospace, aviation, navigation, weaponry, nuclear energy and the like, and in automobile manufacturing. Palladium is used as a precious non-renewable resource, and the recycling of the used palladium is very important. In recent years, various methods such as a chemical precipitation method, an ion exchange and adsorption method, a liquid membrane method, a solvent extraction method, and a leaching resin method have been developed for recovering palladium, and among them, the solvent extraction method is most widely used because of economical efficiency and operability. Therefore, the invention takes the fluorenyl substituent as the raw material to synthesize a class of 9, 9-dipropynyl fluorene and react with mercaptan to generate corresponding polymer, and the corresponding polymer is used for extracting the palladium ion solution.
Disclosure of Invention
The invention aims to provide a high-molecular extracting agent capable of efficiently recovering palladium.
It is another object of the present invention to provide a process for the extraction of metallic palladium which is a one-step extraction process using a single solvent extractant and requiring only one stripping. The invention provides a high molecular extractant compound, which has a general formula as follows:
wherein R = NO2；NH2；CN；H；(CaH2a+1)2N，a=1~4；CmH2m+1M = 1 to 18; n denotes the degree of polymerization.
A method for recovering palladium from an acidic solution using the above extractant, comprising the steps of: preparing an acid solution containing palladium as an aqueous phase, preparing an organic phase containing an extraction component, contacting the aqueous phase with the organic phase for a sufficient time to form a palladium-containing supported organic, and washing and stripping palladium with an acidified thiourea solution to achieve palladium recovery.
The acid solution in the method is 1mol/L hydrochloric acid solution. Preferably, the volume ratio of the aqueous phase to the organic phase is 1: 1.
Organic solvents that may be used in this process include polar hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, esters such as ethyl acetate, chlorobenzene, and 1,2 dichlorobenzene, and the like.
The acidified thiourea solution used in the process can have an acid concentration of about 0.5 to 6M, more preferably about 0.5 to 1M HCl, HNO3，H2SO4HCl is preferred. In addition, the acidified thiourea solution may contain about 0.3 to 1.5M thiourea, such that a concentration of 0.5 to 1M thiourea is preferably achieved.
In solvent extraction technology, the high loading capacity of the extractant plays an important role. In the absence of any modifier, the organic phase employing the extractant disclosed herein can be loaded with high concentrations of palladium in a single batch process without the solvent becoming sticky. Thus, the solvent consumption in the disclosed processes using the novel extractant is much less than the solvent and extractant used in conventional processes
By utilizing the disclosed extractant, the extraction kinetics of palladium are much faster than conventional methods, which shortens the extraction time (180 minutes) for palladium with conventional commercial extractants.
Furthermore, high concentration palladium recovery in the organic phase can be achieved with the process disclosed herein without the use of any modifier conventionally required. Thus, achieving extraction of palladium with the disclosed extractant saves time and energy.
The extraction agent disclosed in the present invention is capable of forming a very stable chelate with palladium, and then recovering the metallic palladium in a stripping stage by means of an acidified thiourea solution. Stripping of the precious metal from the loaded organic phase using acidified thiourea does not destroy the organic phase, as compared to other conventional stripping methods reported in the prior art, such as hydrolysis or direct hydrogen reduction. And the extracting agent used by the invention can be recycled for many times, so the solvent extraction method for efficiently recovering palladium from the acidic solution containing chloride ions by using the novel extracting agent disclosed by the invention can reduce the total cost of precious metal recovery.
Compared with some conventional commercial extractants (DRS and DBC), the disclosed extractants are simple to synthesize, mild in reaction conditions and very low in cost of the synthesis process. Thus, significant improvements are achieved both economically and environmentally due to the advantages of the extractive agents and the resulting processes disclosed above, and have the potential to revolutionize the precious metal recovery industry.
With respect to the above description, it is to be understood that the invention and method herein is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The figure shows the metal extraction method herein. The disclosed processes and disclosed extractants described herein provide a novel one-step precious metal recovery system that can be used in other embodiments and can be implemented in a variety of ways, as will be apparent to those skilled in the art. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting. As such, those skilled in the art will recognize that the concepts upon which the present disclosure is based may readily be used as a basis for designing other improved noble metal extraction processes. It is important, therefore, that the claims and disclosure herein be regarded as including any such equivalent constructions and methods insofar as they do not depart from the spirit of the present invention.
Description of the drawings.
FIG. 1 is a structural diagram of an extractant obtained in example 1.
Fig. 2 is a graph of the loading results for the fresh extractant in example 2.
Figure 3 shows the extraction of palladium as a function of extraction time for the novel extractant of example 3.
Detailed description of the preferred embodiments.
The following examples are given to illustrate the use of the process and extractant disclosed herein.
Example 1: the preparation of a preferred high-molecular extracting agent in the invention comprises the following steps:
(1) in N2Under an atmosphere, fluorene (2g, 12mmol), tetrabutylammonium bromide (0.12g,0.37mmol) and a catalytic amount of KI are sequentially added into a double-neck flask, and then a 50 wt% sodium hydroxide aqueous solution and 3-bromopropyne (2.85 g, 24mmol) are sequentially added for reflux reaction for 5 hours, so that the R-group substituted 9, 9-dipropylenefluorene is prepared.
(2) Weighing 9, 9-dipropynyl fluorene (0.242g, 1mmol) and dissolving in tetrahydrofuran, adding 1wt% of benzophenone and 1, 2-ethanedithiol (0.084 mL, 1mmol) in sequence, and carrying out ultraviolet photopolymerization at 350-400 nm for 1h to obtain the preferable extractant 9, 9-dipropynyl fluorene polythiol. FIG. 1 shows the structure of 9, 9-dipropylfluorene polythiol obtained in example 1.
Example 2: preparing a Pd extraction organic phase by taking HCl concentration of 1mol/L and Pd concentration of 10-400 ppm as a water phase and dichloromethane as a diluent, wherein the concentration of 9, 9-dipropynyl fluorene polythiol in dichloromethane is 1 g/L; and mixing the organic phase and the water phase according to the ratio of 1:1, stirring for 20 minutes, then carrying out phase separation, transferring Pd from the water phase to the organic phase, measuring the concentration of the residual Pd in the water phase, and calculating the loading capacity. The results of the experiment are shown in FIG. 2. It can be seen that the preferred novel extractant of the present invention has a high loading capacity, up to 270 mg/g.
Example 3: preparing a Pd extraction organic phase by using HCl (1 mol/L) and Pd (290 mg/L) as water phases and dichloromethane as a diluent, wherein the concentration of 9, 9-dipropylfluorene polythiol in dichloromethane is 0.7g/L, and preparing 8 parts; respectively mixing and stirring the organic phase and the aqueous phase according to the ratio of 1:1 for 5, 10, 20, 30, 40, 60, 80 and 100 minutes, then separating the phases, transferring Pd from the aqueous phase to the organic phase, measuring the concentration of Pd in the aqueous phase, and calculating the extraction rate. The results of the experiment can be seen in fig. 3, showing that by using the disclosed extractant, the kinetics of extraction of palladium is much faster than the conventional method, requiring only 20 minutes.
Example 4: preparing a Pd extraction organic phase by taking HCl concentration of 1mol/L and Pd concentration of 290mg/L as a water phase and dichloromethane as a diluent, wherein the concentration of 9, 9-dipropynyl fluorene polythiol in dichloromethane is 0.3 g/L; and mixing the organic phase and the water phase according to the ratio of 1:1, stirring for 20 minutes, then carrying out phase separation, transferring Pd from the water phase to the organic phase, measuring the concentration of Pd in the water phase, and calculating the extraction rate, wherein the extraction rate is 60.36%. And (3) placing the Pd-loaded organic phase into a separating funnel, adding 1.0mol/L thiourea into the Pd-loaded organic phase to perform back extraction on the Pd in the organic phase, standing the mixed phase after 10 minutes, measuring the concentration of the Pd in the back extraction phase after phase separation, and calculating the back extraction rate of the Pd in the back extraction by the thiourea, wherein the back extraction rate reaches 94.2%. The results are shown in Table 1.
Example 5: taking HCl with concentration of 1mol/L and Pd with concentration of 290mg/L as a water phase; preparing a Pd extraction organic phase by taking dichloromethane as a diluent and the concentration of 9, 9-dipropynyl fluorene polythiol in the dichloromethane is 0.5 g/L; and mixing the organic phase and the water phase according to the ratio of 1:1, stirring for 20 minutes, then carrying out phase separation, transferring Pd from the water phase to the organic phase, measuring the concentration of Pd in the water phase, and calculating the extraction rate, wherein the extraction rate is 98.04%. And (3) placing the organic phase loaded with Pd in a separating funnel, adding 1.0mol/L thiourea into the organic phase for stripping Pd in the organic phase, standing the mixed phase after 10 minutes, measuring the concentration of Pd in the stripping phase after phase separation, and calculating the stripping rate of Pd stripped by thiourea, wherein the stripping rate reaches 96.6%. The results are shown in Table 1.
Example 6: taking HCl with concentration of 1mol/L and Pd with concentration of 290mg/L as a water phase; preparing a Pd extraction organic phase by taking dichloromethane as a diluent and the concentration of 9, 9-dipropynyl fluorene polythiol in the dichloromethane is 0.7 g/L; and mixing the organic phase and the water phase according to the ratio of 1:1, stirring for 20 minutes, then carrying out phase separation, transferring Pd from the water phase to the organic phase, measuring the concentration of Pd in the water phase, and calculating the extraction rate, wherein the extraction rate is 98.2%. And (3) placing the organic phase loaded with Pd in a separating funnel, adding 1.0mol/L thiourea into the organic phase for stripping Pd in the organic phase, standing the mixed phase after 10 minutes, measuring the concentration of Pd in the stripping phase after phase separation, and calculating the stripping rate of Pd stripped by thiourea, wherein the stripping rate reaches 97.1%. The results are shown in Table 1.
Example 7: taking HCl with concentration of 1mol/L and Pd with concentration of 290mg/L as a water phase; preparing a Pd extraction organic phase by taking dichloromethane as a diluent and the concentration of 9, 9-dipropynyl fluorene polythiol in the dichloromethane is 0.8 g/L; and mixing the organic phase and the water phase according to the ratio of 1:1, stirring for 20 minutes, then separating the phases, transferring Pd from the water phase to the organic phase, measuring the concentration of Pd in the water phase, and calculating the extraction rate, wherein the extraction rate is 98.28. And (3) placing the organic phase loaded with Pd in a separating funnel, adding 1.0mol/L thiourea into the organic phase for stripping Pd in the organic phase, standing the mixed phase after 10 minutes, measuring the concentration of Pd in the stripping phase after phase separation, and calculating the stripping rate of Pd stripped by thiourea, wherein the stripping rate reaches 96.3%. The results are shown in Table 1.
Example 8: taking HCl with the concentration of 3mol/L and Pd with the concentration of 290mg/L as a water phase; preparing a Pd extraction organic phase by taking dichloromethane as a diluent and the concentration of 9, 9-dipropynyl fluorene polythiol in the dichloromethane is 0.9 g/L; and mixing the organic phase and the water phase according to the ratio of 1:1, stirring for 20 minutes, then carrying out phase separation, transferring Pd from the water phase to the organic phase, measuring the concentration of Pd in the water phase, and calculating the extraction rate, wherein the extraction rate is 98.15%. And (3) placing the organic phase loaded with Pd in a separating funnel, adding 1.0mol/L thiourea into the organic phase for stripping Pd in the organic phase, standing the mixed phase after 10 minutes, measuring the concentration of Pd in the stripping phase after phase separation, and calculating the stripping rate of Pd stripped by thiourea, wherein the stripping rate reaches 98.7%. The results are shown in Table 1.
Example 9: taking HCl with concentration of 1mol/L and Pd with concentration of 290mg/L as a water phase; preparing a Pd extraction organic phase by taking dichloromethane as a diluent and the concentration of 9, 9-dipropynyl fluorene polythiol in the dichloromethane is 1.0 g/L; and mixing the organic phase and the water phase according to the ratio of 1:1, stirring for 20 minutes, then separating the phases, transferring Pd from the water phase to the organic phase, measuring the concentration of Pd in the water phase, and calculating the extraction rate, wherein the extraction rate is 98.24%. And (3) placing the organic phase loaded with Pd in a separating funnel, adding 1.0mol/L thiourea into the organic phase for stripping Pd in the organic phase, standing the mixed phase after 10 minutes, measuring the concentration of Pd in the stripping phase after phase separation, and calculating the stripping rate of Pd stripped by thiourea, wherein the stripping rate reaches 96.3%. The results are shown in Table 1.
TABLE 13-10 mg of extractant used for palladium recovery.
Examples 4 to 9 show that the extraction rate of the novel extractant 9, 9-dipropylfluorene polythiol from palladium increases rapidly with increasing amount and reaches saturation in a 1mol/L HCl solution containing 290 mg/L. The extraction agent can well realize the extraction and recovery of the solution containing palladium ions under the condition of extremely low dosage (0.7 g/L), and the extraction rate reaches 98.2 percent and the back extraction rate reaches 97.1 percent. The invention finally selects the dosage of the extractant of 0.7g/L to achieve the highest extraction amount by eliminating errors and based on the principle of saving materials.
While all of the essential features of the extractive agents herein and the resulting processes have been shown and described, numerous modifications, variations and substitutions are intended in the foregoing disclosure and herein, with reference to specific embodiments thereof. It will be apparent that in some instances some features of the present invention may be employed without a corresponding use of other features without departing from the scope of the invention as set forth. It is also to be understood that various substitutions, modifications and changes may be made by those skilled in the art without departing from the spirit or scope of the invention. Accordingly, all such modifications, variations and substitutions which will occur to those skilled in the art upon reading the present disclosure are intended to be included within the scope of the invention as defined by the appended claims.
Claims (6)
1. A polymeric extraction component for recovering palladium from an acidic solution, comprising the following structure:
wherein n denotes the degree of polymerization and the R group is NO2；NH2；CN；H；(CaH2a+1)2N，a=1~4；CmH2m+1，m= 1~18。
2. A method for recovering palladium from an acidic solution using the extractant of claim 1, comprising the steps of: preparing an acid solution containing palladium as an aqueous phase, preparing an organic phase containing an extraction component, contacting the aqueous phase with the organic phase for a sufficient time to form a palladium-containing supported organic, and washing and stripping palladium with an acidified thiourea solution to achieve palladium recovery.
3. The method according to claim 2, characterized in that 1mol/L hydrochloric acid solution is used as the acid solution.
4. The method of claim 2, further comprising: the volume ratio of the water phase to the organic phase is 1: 1.
5. The method according to claim 2, characterized in that the acidified thiourea solution is used, comprising 0.5-6 MHCl.
6. The method of claim 2, further comprising: using the acidified thiourea solution, which contains 0.5-1M thiourea.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481379A (en) * | 2021-06-18 | 2021-10-08 | 金川集团股份有限公司 | Method for removing impurities by using palladium extracting agent |
| CN114959289A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Method for recovering platinum from palladium extraction organic phase |
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| JP2019123806A (en) * | 2018-01-17 | 2019-07-25 | 公立大学法人大阪府立大学 | Curable composition and cured product thereof and method for producing cured product |
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| WO2016073052A1 (en) * | 2014-11-03 | 2016-05-12 | Life Technologies Corporation | Dibenzosilole monomers and polymers and methods for their preparation and use |
| JP2019123806A (en) * | 2018-01-17 | 2019-07-25 | 公立大学法人大阪府立大学 | Curable composition and cured product thereof and method for producing cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113481379A (en) * | 2021-06-18 | 2021-10-08 | 金川集团股份有限公司 | Method for removing impurities by using palladium extracting agent |
| CN113481379B (en) * | 2021-06-18 | 2022-08-12 | 金川集团股份有限公司 | Method for removing impurities by using palladium extracting agent |
| CN114959289A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Method for recovering platinum from palladium extraction organic phase |
| CN114959289B (en) * | 2022-04-25 | 2023-09-29 | 金川集团股份有限公司 | Method for recovering platinum in palladium extraction organic phase |
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