CN104524808B - 3-sulfur glutaramide kind of extractants and the application in extraction of palladium thereof - Google Patents

3-sulfur glutaramide kind of extractants and the application in extraction of palladium thereof Download PDF

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CN104524808B
CN104524808B CN201410837881.2A CN201410837881A CN104524808B CN 104524808 B CN104524808 B CN 104524808B CN 201410837881 A CN201410837881 A CN 201410837881A CN 104524808 B CN104524808 B CN 104524808B
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黄瑛
武剑
李泳华
李尚华
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Southeast University
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Abstract

The invention discloses a kind of 3-sulfur glutaramide kind of extractants. The present invention proposes the preparation method and application of above-mentioned extractant simultaneously. First pass through methanol and be obtained by reacting dimethly thiodiglycolate with thiodiglycolic acid, finally make corresponding amine and dimethly thiodiglycolate be obtained by reacting corresponding 3-sulfur glutaramide. The extraction efficiency of precious metal palladium is 98.16%��99.22% by the extractant of the present invention. This extractant can apply simultaneously to Recover palladium in the mixed solution containing palladium, platinum, copper and the base metal such as ferrum, zinc. The preparation method of the present invention is simple, and has superior extraction ability for the palladium ion in high acid solution, and strong acid is stable, and irradiation stability is good, and synthetic method is simple, and cost is low.

Description

3-thioglutaramide extracting agent and application thereof in palladium extraction
Technical Field
The invention belongs to the technical field of precious metal extraction, and particularly relates to a 3-thioglutaramide extracting agent and application thereof in palladium extraction.
Background
A large amount of electronic wastes are generated every year in China, the quantity of the electronic wastes is continuously increased along with the updating and upgrading of electronic products, and the unreasonable disposal of the large amount of electronic wastes not only pollutes the environment, but also causes huge resource waste. The purity of some parts or parts of the electronic waste plated with palladium is very high, for example, the purity of some palladium elements can reach 99.999 percent, so that the recovery of noble metals from the electronic waste is in great trend. The precipitation method and the displacement method are traditional processes for separating and recovering the noble metals, the processes are complex, the energy consumption is high, and the solvent extraction method is considered as the most promising method for recovering the noble metals due to good separation effect, short period and simple process.
The extractant is the core of solvent extraction, and mainly adopts thioether and sulfoxide at home and abroadThe noble metal is recovered by treating with the extractant, which is a traditional extractant and has some problems such as poor acid resistance, long extraction equilibrium time and the like. Particularly, after the electronic waste is subjected to acid leaching, the acid leaching solution contains noble metals such as Au and the like. However, the extraction efficiency of the existing extractant is sharply reduced under the condition of high acid concentration. In patent application No. 201110257876.0, a process for the synthesis of an extractant in the form of a dialkyl diglycol amide of the general structural formula(R1、R2Is an independent alkyl group); diamide compound (R) is described in patent publication No. CN102020579A1R2NCO)2CH2OCH2(R1、R2Is an independent alkyl group), and the diamide compound belongs to oxoglutaramide.
Disclosure of Invention
The purpose of the invention is as follows: in order to avoid the problems of acid resistance, long extraction balance time and the like when the thioether and sulfoxide extractants recover precious metals, the invention provides a 3-thioglutaramide extractant, and the invention also aims to solve the technical problem of providing a preparation method and application of the extractant.
The technical scheme is as follows: in order to achieve the technical purpose, the invention provides a 3-thioglutaramide extracting agent which has the following structural formula:
R1is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms; r2Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or a cyclic substituent having 6 carbon atoms14 aromatic substituents. Preferably, R is1And R2Respectively an aliphatic chain substituent having 1 to 9 carbon atoms or an aromatic substituent having 6 to 12 carbon atoms.
The invention further provides a preparation method of the 3-thioglutaramide extracting agent, which comprises the following steps:
(1) preparation of dimethyl 2, 2' -thiodiglycolate: dissolving 2,2 ' -thiodiglycolic acid in methanol to obtain a methanol solution of the 2,2 ' -thiodiglycolic acid, heating and keeping the temperature at 5-100 ℃, stirring for 3-15 h, standing and cooling to room temperature, removing the methanol by rotary evaporation, and then performing vacuum suction to remove the residual methanol to obtain crude dimethyl 2,2 ' -thiodiglycolate;
(2) preparation of 2, 2' -3-thioglutaryl amide: respectively preparing a trichloromethane solution of amine and a trichloromethane solution of a crude product of dimethyl thiodiglycolate, dropwise adding the trichloromethane solution of the crude product of dimethyl thiodiglycolate into the trichloromethane solution of amine, reacting at 20-100 ℃, continuing to react at 50-300 ℃ for 2.5-8 h after dropwise adding is finished, and sequentially reacting the reacted mixture with an HCl solution and Na2CO3Repeatedly washing the solution with distilled water to neutrality, and separating the organic layer with Na2SO4Drying, evaporating chloroform from filtrate after suction filtration by using a rotary evaporator, and then recrystallizing for 2-3 times by using ethyl acetate to obtain a crystallized product, wherein the amine has the following structural formula:
wherein R is1Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms; r2Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms. Preferably, R is1And R2Respectively an aliphatic chain substituent having 1 to 9 carbon atoms or an aromatic substituent having 6 to 12 carbon atoms.
In the step (1), the material molar ratio of the 2,2 '-thiodiglycolic acid to the methanol is 1 (2-3), and preferably the material molar ratio of the 2, 2' -thiodiglycolic acid to the methanol is 1: 2.5.
In the step (2), the material molar ratio of the dimethyl 2,2 '-thio-diglycinate to the amine is 1 (2-3), preferably, the material molar ratio of the dimethyl 2, 2' -thio-diglycinate to the amine is 1: 2.5.
preferably, in the step (2), the concentration of the HCl solution is 0.1-5 mol/L, and Na is added2CO3The concentration of the solution is 0.1-25 wt%, HCl solution and Na2CO3The usage amount of the solution and the distilled water is 1-1.5 times of the volume of the mixture after the reaction.
The invention further provides application of the 3-thioglutaramide extracting agent in palladium extraction.
Specifically, the method comprises the following steps: dissolving 3-thioglutaramide extracting agent in an organic solvent to obtain an extraction liquid, and treating an aqueous solution containing palladium by using the extraction liquid in the presence of an acidic solution.
The acid solution is hydrochloric acid, and the concentration of the hydrochloric acid is 1-9 mol/L.
The invention also provides application of the 3-sulfur glutaramide extracting agent in extracting palladium in the mixed solution containing palladium, platinum, copper, iron and zinc ions.
Specifically, the method comprises the following steps: dissolving a 3-thioglutaramide extracting agent in an organic solvent to obtain an extraction liquid, removing copper, iron and zinc from a mixed solution containing palladium, platinum, copper, iron and zinc ions by a precipitation method to obtain a mixed solution containing palladium and platinum, extracting the mixed solution containing palladium and platinum by using the extraction liquid, and contacting the separated organic phase with hydrochloric acid to carry out back extraction to obtain an aqueous solution containing palladium.
Has the advantages that: compared with the prior art, the preparation method of the N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide extractant provided by the invention is simple and feasible, has excellent extraction performance on palladium ions in a high-acid solution, is stable to strong acid, has good irradiation stability, and is simple in synthesis method and low in cost.
Drawings
FIG. 1 is an infrared spectrum of N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide;
FIG. 2 is a schematic representation of N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide1A HNMR map;
FIG. 3 is a schematic representation of N, N '-dimethyl-N, N' -diphenyl-3-oxoglutaramide13A CNMR map.
Detailed Description
The invention provides a 3-sulfur glutaramide extractant, which has the following structural formula:
wherein R is1Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms; r2Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms.
The preparation method of the 3-thioglutaramide extracting agent comprises the following steps:
(1) preparation of dimethyl 2, 2' -thiodiglycolate: dissolving 2,2 '-thiodiglycolic acid with methanol to obtain a methanol solution of the 2, 2' -thiodiglycolic acid, wherein the material molar ratio of the 2,2 '-thiodiglycolic acid to the methanol is 1 (2-3), heating and maintaining at 5-100 ℃, stirring for 3-15 h, standing and cooling to room temperature, removing the methanol by rotary evaporation, and then performing vacuum suction to remove residual methanol to obtain crude dimethyl 2, 2' -thiodiglycolate;
(2) preparation of 2, 2' -3-thioglutaryl amide: respectively preparing a trichloromethane solution of amine and a trichloromethane solution of a crude product of dimethyl thiodiglycolate, dropwise adding the trichloromethane solution of the crude product of dimethyl thiodiglycolate into the trichloromethane solution of amine, wherein the molar ratio of dimethyl 2, 2' -thiodiglycolate to amine is 1 (2-3), reacting at 20-100 ℃, continuously reacting at 50-300 ℃ for 2.5-8 h after dropwise adding, and sequentially using an HCl solution and Na for reacting the reacted mixture2CO3Repeatedly washing the solution and distilled water to be neutral, wherein the concentration of HCl solution is 0.1-5 mol/L, and Na is2CO3The concentration of the solution is 0.1-25 wt%, HCl solution and Na2CO3The dosage of the solution and distilled water is 1-1.5 times of the volume of the mixture after reaction, and Na is used for an organic layer obtained after phase separation2SO4Drying, evaporating chloroform from filtrate after suction filtration by using a rotary evaporator, and then recrystallizing for 2-3 times by using ethyl acetate to obtain a crystallized product, wherein the amine has the following structural formula:
wherein R is1Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms; r2Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms. .
The present invention will be described in detail below with reference to specific examples. Wherein R is1And R2Respectively methyl and phenyl.
Example 1 preparation of N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide.
Adding 2, 2' -thiodiglycolic acid into a three-neck flask, and dissolving with methanol; stirring and reacting for 5 hours at 50 ℃; the reaction solution was cooled to room temperature, and the reaction solution was transferred to an eggplant-shaped flask, excess methanol was removed by a rotary evaporator, followed by vacuum suction to remove a trace amount of residual methanol, to obtain dimethyl 2, 2' -thiodiglycolate with a yield of 85%.
Adding methylaniline into a three-neck flask with a constant-pressure funnel, dissolving the methylaniline by using trichloromethane, dissolving the obtained 2, 2' -sulfo-diglycolic acid dimethyl ester by using the trichloromethane, and transferring the solution into a constant-pressure funnel; the three-necked flask was placed in a water bath at 40 ℃ and a chloroform solution of thiodiglycolic chloride was added dropwise at a rate of 1 drop per 1 second. After the completion of the dropwise addition, the reaction was stirred at 140 ℃ for 3 hours.
Cooling the obtained reaction solution to room temperature, adding cold water into a beaker, adding the cooled reaction solution into the beaker, fully stirring, and standing by using a separating funnel to separate an organic phase from a water phase. Adding distilled water into the separated organic phase, oscillating the separating funnel, and separating the organic phase from the water phase; the organic phase obtained was separated twice with 1.0mol/L hydrochloric acid solution, twice with distilled water, twice with 5 wt% sodium carbonate aqueous solution, and finally washed with distilled water for several times until the pH of the aqueous phase after phase separation became 7. The organic phase after washing was transferred to an eggplant-shaped flask, and Na was added thereto2SO4The organic phase was stirred for two hours to remove residual water.
The crystallized sodium sulfate was filtered off, the filtrate was transferred to an eggplant-shaped flask, and the solvent was removed from the eggplant-shaped flask on a rotary evaporator, followed by vacuum suction to remove the remaining solution. To remove insoluble matter, recrystallization 2 to 3 times using ethyl acetate; the extractant product was obtained in 67% yield.
The prepared extractants were characterized and the results are shown in fig. 1 to 3.
FIG. 1 is an infrared spectrum of N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide. The main absorption peaks were assigned: at 2903cm-1The peak at (a) indicates stretching vibration of a saturated C — H bond with ═ C-H, and is generally a methyl group; 1496cm-1The peak at position (d) is generated by stretching vibration of the whole C ═ C bond of the benzene ring, and is a characteristic peak of aromatic skeleton vibration. At 770cm-1The peak at (a) illustrates out-of-plane bending vibration with aromatic ring ═ C — H. The presence of both peaks indicates the presence of an aromatic compound having five adjacent hydrogens, i.e., a monosubstituted benzene nucleus; 1664cm-1The peak is a carbonyl stretching vibration absorption peak, which shows the deformation vibration absorption of methyl and methylene; 1250cm-1Is a C-S-C asymmetric stretching vibration absorption peak.
FIG. 2 is a graph of N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide in deuterated chloroform1The H-NMR spectrum and the chemical shifts of the individual protons are shown in Table 2.3. As can be seen from the structural diagram in fig. 2.9, under the influence of other groups, H in the molecule can be classified into 4 types, namely: 1, -N-CH3H above; 3, -CH2-H on S; 5, H in the benzene ring, which is ortho to other groups; 6, 7, H which is not ortho-position with other groups in the benzene ring; positions 2,4 have no H. From the integral curve in fig. 2.8, the ratio of the hydrogen atoms is 6:4:6:4, and the hydrogen atoms and peak types corresponding to the peak groups in the hydrogen spectrum indicate the symmetry of the molecule.
H(400MHz,CDCl3):3.232,3.298(6H,-CH3-N)，3.406(4H，-CH2-S-)，7.225-7.421(10H,-CH)。
FIG. 3 is a schematic representation of N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide13CNMR spectrum, 1-5 in Table 1 represents hydrogen corresponding to 1-5 carbon atoms in the structure diagram of the extractant. The peaks at 76.761-77.396ppm correspond to the chemical shifts of C in the solvent deuterated chloroform; the peak at 169.208ppm corresponds to the signal for two carbonyl carbons in the compound (i.e., position 2); 37.645ppm of peak corresponds to N-CH3Chemical shift of the middle carbon (i.e., position 1), the peak at 33.817ppm corresponds to S-CH2Carbon signal (i.e. position 3), 127.093ppm,128.203ppm,129.914ppm is the chemical shift of the carbon in the benzene ring (i.e.positions 4-7).
C(400MHz，DMSO)：37.645(2C，CH3-N-)，33.817(2C,-CH2-S),127.415,127.740,129.864(2C,-CH)，169.208(2C，-C＝O)。
The structural formula of the N, N '-dimethyl-N, N' -diphenyl-3-thioglutaramide is as follows:
TABLE 1 chemical shifts of N, N '-dimethyl-N, N' -diphenyl-3-thioglutarylamide proton hydrogens
Example 2 testing of the equilibration time for an extractant to extract noble metal palladium.
The reaction product prepared in example 1 was dissolved in a chloroform system to form a chloroform solution having an extractant concentration of 0.02mol/L, and an aqueous solution of palladium chloride was prepared as an organic phase so that the concentration of palladium was 50mg/L, and an extraction test was conducted as an aqueous phase. Wherein, the volumes of the organic phase and the aqueous phase are respectively 5mL in a conical flask and are oscillated in a water bath constant temperature oscillator until extraction balance is achieved, the concentration of hydrochloric acid is controlled to be 3mol/L in the extraction process, the amplitude is controlled to be 160 +/-2 spm, the extraction temperature is controlled to be 25 +/-0.5 ℃, the organic phase and the aqueous phase are transferred to a centrifuge tube for centrifugal phase separation after oscillation is finished, and the concentration of metal ions in the aqueous phase after phase separation is measured by ICP-OES.
Wherein,
the extraction partition ratio is represented by D,
the extraction efficiency is expressed in E (%),
the efficiency of the back-extraction was expressed in E' (%),
Coconcentration of metal ions in the starting aqueous solution
CiConcentration of aqueous phase metal ions after extraction
Ci' -concentration of metal ions in aqueous phase after back extraction
The extraction efficiency of Pd (II) at different extraction times is shown in Table 2.
TABLE 2 extraction efficiency of Pd (II) by the extractant at different extraction times
As can be seen from Table 2, the optimum extraction equilibrium time for Pd (II) was 90min, and the optimum extraction efficiency for Pd (II) was 99.48%.
Example 3 test experiment of the effect of hydrochloric acid concentration on the extraction performance of a synthetic extractant.
Dissolving the extractant N, N '-dimethyl-N, N' -diphenyl-3-thioglutamide prepared in the example 1 into a trichloromethane system to form a trichloromethane solution with the concentration of the extractant of 0.02mol/L as an organic phase; an aqueous solution of palladium chloride was prepared so that the concentration of palladium was 50mg/L, and an extraction test was carried out as an aqueous phase. 5mL of organic phase and water phase are respectively taken, the organic phase and the water phase are oscillated in a conical flask in a water bath constant temperature oscillator until extraction balance is achieved, the amplitude is 160 +/-2 spm, the extraction temperature is controlled to be 25 +/-0.5 ℃, the concentration of hydrochloric acid is controlled to be 1-mol/L in the extraction process, the organic phase and the water phase are transferred to a centrifugal tube for centrifugal phase separation after oscillation is finished, and the concentration of metal ions in the water phase after phase separation is measured by ICP-OES.
After shaking for a sufficient period of time for extraction equilibrium, the extraction efficiency for Pd (II) at different concentrations of hydrochloric acid is shown in Table 3.
TABLE 3 extraction efficiency of Pd (II) by the extractant at different hydrochloric acid concentrations
As can be seen from Table 3, the extraction of Pd (II) reached 99.22% already at low acidity, and then remained substantially unchanged with increasing hydrochloric acid concentration, with greater resistance to strong acids.
Example 4 test experiment of the effect of aqueous phase hydrogen ion concentration on extraction efficiency.
Dissolving the extractant N, N '-dimethyl-N, N' -diphenyl-3-thioglutamide prepared in the example 1 into a trichloromethane system to form a trichloromethane solution with the concentration of the extractant of 0.02mol/L as an organic phase; an aqueous solution of palladium chloride was prepared so that the concentration of palladium was 50mg/L, and as an aqueous phase, lithium chloride was added so as to maintain the chloride ion concentration of the aqueous phase at 3mol/L, and the H + concentrations were adjusted to 1.36, 1.63, 2.12, 2.46, 2.82, and 3.23, respectively, to conduct extraction tests. 5mL of organic phase and water phase are respectively taken, the organic phase and the water phase are oscillated in a conical flask in a water bath constant temperature oscillator until extraction balance is achieved, the amplitude is 160 +/-2 spm, the extraction temperature is controlled to be 25 +/-0.5 ℃, the concentration of hydrochloric acid is controlled to be 1-mol/L in the extraction process, the organic phase and the water phase are transferred to a centrifugal tube for centrifugal phase separation after oscillation is finished, and the concentration of metal ions in the water phase after phase separation is measured by ICP-OES.
After shaking for a sufficient time to extract equilibrium, the extraction efficiency for Pd (II) at different concentrations of hydrogen ions in the aqueous phase is shown in Table 4.
TABLE 4 extraction efficiency of Pd (II) by the synthetic extractant at different concentrations of aqueous phase hydrogen ions
Example 5 performance test experiments for extracting different metals with extractant at different hydrochloric acid concentrations.
The extraction test was performed by dissolving the extractant N, N '-dimethyl-N, N' -diphenyl-3-thioglutarylamide prepared in example 1 in a chloroform system to form a chloroform solution with a concentration of the extractant of 0.02mol/L, as an organic phase, and dissolving palladium chloride, iron chloride, platinum chloride, zinc chloride, and copper chloride in water to obtain aqueous solutions of metals as an aqueous phase, each of which has a concentration of 50 mg/L. The volume ratio of the water phase to the organic phase is 1:1, the volume ratio of the organic phase to the water phase is 5mL respectively, the water phase and the water phase are oscillated in a water bath constant temperature oscillator for 90min in a conical flask to reach extraction balance, the amplitude is 160 +/-2 spm, the extraction temperature is controlled to be 25 +/-0.5 ℃, the mixture is transferred into a centrifugal tube for centrifugal phase separation after oscillation is finished, and the concentration of metal ions in the water phase after phase separation is measured by ICP-OES.
The effect of aqueous hydrochloric acid concentration on the extraction efficiency of N, N '-dimethyl-N, N' -diphenyl-3-thioglutamide (DMDPhTDGA) for extraction of Pt (iv), pd (ii), Fe (iii), zn (ii), cu (ii) is shown in table 5. As shown in Table 5, the extraction rates of Pd (II) and Pd (II) are high and higher than 99.0% at a hydrochloric acid concentration of <4mol/L, but the extraction rates of other Pt (IV), Fe (III), Zn (II) and Cu (II) are low and lower than 7.1%, and the extraction rates of Fe (III), Zn (II) and Cu (II) are increased greatly and are not beneficial to separating Pd (II) at a hydrochloric acid concentration of >5 mol/L. Therefore, when Pd (II) is separated from the mixed solution of Pt (IV), Pd (II), Fe (III), Zn (II), and Cu (II), the hydrochloric acid concentration should be kept at <4 mol/L.
TABLE 5 influence of DMDPHTHDGA on the extraction efficiency of Pt (IV), Pd (II), Fe (III), Zn (II), Cu (II)
Example 6 test of extraction of palladium from a mixed solution by an extractant.
The extraction test was performed by dissolving the extractant N, N '-dimethyl-N, N' -diphenyl-3-thioglutarylamide prepared in example 1 in a chloroform system to form a chloroform solution with a concentration of the extractant of 0.02mol/L, as an organic phase, and dissolving palladium chloride, iron chloride, platinum chloride, zinc chloride, and copper chloride in water to obtain aqueous solutions of metals as an aqueous phase, each of which has a concentration of 50 mg/L.
NaOH was added to the aqueous solution so that the concentration of NaOH was 1mol/L, and a precipitate was formed in the solution, which was then filtered through a filter paper to remove Fe (III), Zn (II), and Cu (II) ions. The pH of the filtered aqueous solution was adjusted to 7 by adding hydrochloric acid solution, and then hydrochloric acid was added to adjust the hydrochloric acid concentration in the aqueous solution to 3 mol/L.
Mixing the aqueous solution and the organic phase, wherein the volume ratio of the aqueous phase to the organic phase is 1:1, the volume ratio of the organic phase to the aqueous phase is 5mL respectively, oscillating the mixture in a conical flask in a water bath constant temperature oscillator for 90min to reach extraction equilibrium, controlling the amplitude to be 160 +/-2 spm, controlling the extraction temperature to be 25 +/-0.5 ℃, and transferring the mixture to a centrifugal tube for centrifugal phase separation after oscillation is finished. The metal ion concentration of the aqueous phase after phase separation was determined by ICP-OES. The extraction rate of the extractant on Pd (II) is 99.3 percent, and the extraction rate of the extractant on Pt (IV) is 3.2 percent respectively.
And mixing the extracted organic phase with 0.1mol/L hydrochloric acid solution for back extraction. The volume ratio of the water phase to the organic phase is 1:1, the organic phase and the water phase are respectively 5mL, and the mixture is oscillated in a water bath constant temperature oscillator for 90min in a conical flask to reach the back extraction equilibrium, the amplitude is 160 +/-2 spm, the back extraction temperature is controlled to be 25 +/-0.5 ℃, and the mixture is transferred to a centrifuge tube for centrifugal phase separation after the oscillation is finished. The metal ion concentration of the aqueous phase after phase separation was determined by ICP-OES. The stripping rate of Pd (II) by 0.1mol/L hydrochloric acid solution was 96.1%.

Claims (4)

1. A preparation method of 3-thioglutaramide extractant is characterized in that the extractant has the following structural formula:
wherein R is1Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms; r2Is C1-9 or C more than 11The aliphatic chain substituent, the aliphatic ring substituent with 4-10 carbon atoms or the aromatic substituent with 6-14 carbon atoms, and the preparation method of the 3-thioglutaramide extracting agent comprises the following steps:
(1) preparation of dimethyl 2, 2' -thiodiglycolate: dissolving 2,2 ' -thiodiglycolic acid in methanol to obtain a methanol solution of the 2,2 ' -thiodiglycolic acid, heating and keeping the temperature at 5-100 ℃, stirring for 3-15 h, standing and cooling to room temperature, removing the methanol by rotary evaporation, and then performing vacuum suction to remove the residual methanol to obtain crude dimethyl 2,2 ' -thiodiglycolate;
(2) preparation of 2, 2' -3-thioglutaryl amide: respectively preparing a trichloromethane solution of amine and a trichloromethane solution of a crude product of dimethyl thiodiglycolate, dropwise adding the trichloromethane solution of the crude product of dimethyl thiodiglycolate into the trichloromethane solution of amine, reacting at 20-100 ℃, continuing to react at 50-300 ℃ for 2.5-8 h after dropwise adding is finished, and sequentially reacting the reacted mixture with an HCl solution and Na2CO3Repeatedly washing the solution with distilled water to neutrality, and separating the organic layer with Na2SO4Drying, evaporating chloroform from filtrate after suction filtration by using a rotary evaporator, and then recrystallizing for 2-3 times by using ethyl acetate to obtain a crystallized product, wherein the amine has the following structural formula:
wherein R is1Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms; r2Is an aliphatic chain substituent having 1 to 9 carbon atoms or more than 11 carbon atoms, an aliphatic cyclic substituent having 4 to 10 carbon atoms or an aromatic substituent having 6 to 14 carbon atoms.
2. The preparation method according to claim 1, wherein in the step (1), the molar ratio of the 2, 2' -thiodiglycolic acid to the methanol is 1: 2-3.
3. The preparation method according to claim 1, wherein in the step (2), the feed molar ratio of the 2, 2' -dimethylthiodiglycolate to the amine is 1: 2-3.
4. The method according to claim 1, wherein in the step (2), the concentration of the HCl solution is 0.1-5 mol/L, and Na is added2CO3The concentration of the solution is 0.1-25 wt%, HCl solution and Na2CO3The usage amount of the solution and the distilled water is 1-1.5 times of the volume of the mixture after the reaction.
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