CN104524808A - 3-sulfoglutaramide type extraction agent and application thereof in extraction of palladium - Google Patents

3-sulfoglutaramide type extraction agent and application thereof in extraction of palladium Download PDF

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CN104524808A
CN104524808A CN201410837881.2A CN201410837881A CN104524808A CN 104524808 A CN104524808 A CN 104524808A CN 201410837881 A CN201410837881 A CN 201410837881A CN 104524808 A CN104524808 A CN 104524808A
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palladium
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sulphur
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CN104524808B (en
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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 3-sulfoglutaramide type extraction agent. The invention simultaneously provides a preparation method and application of the extraction agent. The preparation method comprises the following steps: firstly reacting methanol with thiodiacetic acid to obtain dimethyl thiodiacetate, and finally reacting corresponding amine with dimethyl thiodiacetate to obtain corresponding 3-sulfoglutaramide. The extraction efficiency of the extraction agent against a precious metal, namely palladium, is 98.16%-99.22%. The extraction agent can be simultaneously applied to a mixed solution containing palladium, platinum, copper, iron, zinc and other base metals for recovering palladium. The preparation method disclosed by the invention is simple and easy to operate, and the extraction agent has excellent extraction performance against palladium ions in a high-acid solution; and furthermore, the extraction agent is stable to a strong acid and good in radiation stability, the synthesis method is simple, and the cost is low.

Description

3-sulphur glutaramide kind of extractants and the application in extraction of palladium thereof
Technical field
The invention belongs to noble metal abstraction technique field, relate to a kind of 3-sulphur glutaramide kind of extractants and the application in extraction of palladium thereof particularly.
Background technology
China produces a large amount of electron wastes every year, and along with the update of electronic product, electron wastes quantity constantly increases, the unreasonable disposal not only contaminated environment of a large amount of electron wastes, and causes the huge wasting of resources.In electron wastes, to plate the metal purity of palladium outward very high for some parts or parts, and the purity of such as some palladium elements can reach 99.999%, so reclaiming noble metal from electron wastes is trend of the times.The precipitation method and displacement method are the traditional handicrafts of separation and recovery noble metal, and technique is miscellaneous, energy consumption is large, solvent extraction because of its good separating effect, the cycle is short, technique is simple and be considered to the method for the most promising recovery noble metal.
Extractant is solvent-extracted core, mainly both at home and abroad adopts thioether class and the process of sulfoxide two kind of extractants to reclaim noble metal, and these extractants are all traditional extractants, exist some problems if not acidproof, the extraction equilibrium time is long.Particularly electron wastes is after Ore Leaching, containing noble metals such as Au in acid leaching solution.But existing extractant is under high acid concentration, and extraction efficiency sharply declines.Describe the method for the extractant of synthesis dialkyl group diethylene glycol (DEG) amide form thereof in number of patent application 201110257876.0, the general structure of the material of the type is (R 1, R 2for independently alkyl); Diamide compound (R is described in license publication number CN 102020579A 1r 2nCO) 2cH 2oCH 2(R 1, R 2for independently alkyl) synthetic method, this diamide compound belongs to oxygen glutaramide.
Summary of the invention
Goal of the invention: the problem such as not acidproof when reclaiming noble metal for avoiding thioether class and sulfoxide two kind of extractants, the extraction equilibrium time is long, the invention provides 3-sulphur glutaramide kind of extractants, the technical problem that the present invention also will solve is to provide the preparation method and application of above-mentioned extractant.
Technical scheme: for realizing above-mentioned technical purpose, the invention provides a kind of 3-sulphur glutaramide kind of extractants, described extractant has following structural formula:
R 1for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11; R 2for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11.Preferably, preferably, R 1and R 2be respectively the aliphatic chain substituting group of carbon number 1 ~ 9 or the aromatic substituents of carbon number 6 ~ 12.
Present invention further proposes the preparation method of above-mentioned 3-sulphur glutaramide kind of extractants, comprise the steps:
(1) 2, the preparation of 2 '-dimethly thiodiglycolate: 2,2 '-thiodiglycolic acid methyl alcohol is dissolved and obtains 2, the methanol solution of 2 '-thiodiglycolic acid, heat and remain on 5 ~ 100 DEG C, stir 3 ~ 15h, place and cool to room temperature, rotary evaporation removes methyl alcohol, then vacuum draw, remove residual methyl alcohol, obtain rough 2,2 '-dimethly thiodiglycolate;
(2) 2, the preparation of 2 '-3-sulphur glutaramide: prepare the chloroform soln of amine and the chloroform soln of the thick product of dimethly thiodiglycolate respectively, then the chloroform soln of thick for dimethly thiodiglycolate product is added drop-wise in the chloroform soln of amine, react at 20 ~ 100 DEG C, dropwise rear continuation and at 50 ~ 300 DEG C, react 2.5 ~ 8h reacted mixture is used HCl solution, Na successively 2cO 3solution and distilled water cyclic washing are extremely neutral, the organic layer Na obtained after phase-splitting 2sO 4drying, chloroform steaming removes with Rotary Evaporators by the filtrate after suction filtration, and then use re-crystallizing in ethyl acetate 2 ~ 3 times, obtain crystallized product, wherein, described amine has following structural formula:
Wherein, R 1for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11; R 2for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11.Preferably, preferably, R 1and R 2be respectively the aliphatic chain substituting group of carbon number 1 ~ 9 or the aromatic substituents of carbon number 6 ~ 12.
Wherein, in step (1), 2, the molar ratio of material of 2 '-thiodiglycolic acid and methyl alcohol is 1:(2 ~ 3), preferably, 2, the molar ratio of material of 2 '-thiodiglycolic acid and methyl alcohol is 1:2.5.
In step (2), 2, the molar ratio of material of 2 '-dimethly thiodiglycolate and amine is 1:(2 ~ 3), preferably, 2, the molar ratio of material 1:2.5 of 2 '-dimethly thiodiglycolate and amine.
Preferably, in step (2), the concentration of HCl solution is 0.1 ~ 5mol/L, Na 2cO 3the concentration of solution is 0.1 ~ 25wt%, HCl solution, Na 2cO 3the consumption of solution and distilled water is 1 ~ 1.5 times of the volume of mixture after reaction.
Present invention further proposes the above-mentioned application of 3-sulphur glutaramide kind of extractants in extraction of palladium.
Particularly, comprise the steps: 3-sulphur glutaramide kind of extractants to be dissolved in organic solvent to be extracted liquid, under acid solution existent condition, with described extract to the aqueous solution containing palladium.
Wherein, described acid solution is hydrochloric acid, and the concentration of described hydrochloric acid is 1 ~ 9mol/L.
The invention allows for 3-sulphur glutaramide kind of extractants comprises the palladium in palladium, platinum, copper, iron and zinc ion mixed solution application in extraction.
Particularly, comprise the steps: 3-sulphur glutaramide kind of extractants to be dissolved in organic solvent to be extracted liquid, the mixed solution precipitation method containing palladium, platinum, copper, iron and zinc ion are removed copper, iron, zinc, obtain the mixed liquor containing palladium and platinum, then with above-mentioned extract, the mixed liquor containing palladium and platinum is extracted, the organic phase of separation is contacted with hydrochloric acid and strips, obtain the aqueous solution containing palladium.
Beneficial effect: compared with prior art, the N that the present invention proposes, N '-dimethyl-N, the preparation method of N '-diphenyl-3-sulphur glutaramide extractant is simple, and for the palladium ion in high acid solution, there is superior extraction ability, and strong acid is stablized, irradiation stability is good, synthetic method is simple, and cost is low.
Accompanying drawing explanation
Fig. 1 is N, the infrared spectrogram of N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide;
Fig. 2 is N, N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide 1h NMR schemes;
Fig. 3 is N, N '-dimethyl-N, N '-diphenyl-3-oxygen glutaramide 13c NMR schemes.
Detailed description of the invention
The invention provides a class 3-sulphur glutaramide extractant, structural formula is as follows:
Wherein, R 1for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11; R 2for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11.
The preparation method of above-mentioned 3-sulphur glutaramide kind of extractants comprises the steps:
(1) 2, the preparation of 2 '-dimethly thiodiglycolate: 2,2 '-thiodiglycolic acid methyl alcohol is dissolved and obtains 2, the methanol solution of 2 '-thiodiglycolic acid, 2, the molar ratio of material of 2 '-thiodiglycolic acid and methyl alcohol is 1:(2 ~ 3), heat and remain on 5 ~ 100 DEG C, stir 3 ~ 15h, place and cool to room temperature, rotary evaporation removes methyl alcohol, then vacuum draw, remove residual methyl alcohol, obtain rough 2,2 '-dimethly thiodiglycolate;
(2) 2, the preparation of 2 '-3-sulphur glutaramide: prepare the chloroform soln of amine and the chloroform soln of the thick product of dimethly thiodiglycolate respectively, then the chloroform soln of thick for dimethly thiodiglycolate product is added drop-wise in the chloroform soln of amine, 2, the molar ratio of material of 2 '-dimethly thiodiglycolate and amine is 1:(2 ~ 3), react at 20 ~ 100 DEG C, dropwise rear continuation and at 50 ~ 300 DEG C, react 2.5 ~ 8h reacted mixture is used HCl solution, Na successively 2cO 3solution and distilled water cyclic washing are to neutral, and the concentration of HCl solution is 0.1 ~ 5mol/L, Na 2cO 3the concentration of solution is 0.1 ~ 25wt%, HCl solution, Na 2cO 3the consumption of solution and distilled water is 1 ~ 1.5 times of the volume of mixture after reaction, the organic layer Na obtained after phase-splitting 2sO 4drying, chloroform steaming removes with Rotary Evaporators by the filtrate after suction filtration, and then use re-crystallizing in ethyl acetate 2 ~ 3 times, obtain crystallized product, wherein, described amine has following structural formula:
Wherein, R 1for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11; R 2for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11.。
The present invention is described in detail below by specific embodiment.Wherein, R 1and R 2be respectively methyl and phenyl.
Embodiment 1N, the preparation of N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide.
In there-necked flask, add 2,2 '-thiodiglycolic acid, dissolve with methyl alcohol; Stirring reaction 5 hours at 50 DEG C; Placement is cooled to room temperature, and reaction solution is moved into eggplant type flask, is removed by the methyl alcohol of surplus, then vacuum draw with rotary evaporator, the Trace Methanol that removing is residual, and namely obtain 2,2 '-dimethly thiodiglycolate, productive rate is 85%.
In the there-necked flask having constant pressure funnel, add methylaniline and dissolve with chloroform, will obtain 2,2 '-dimethly thiodiglycolate chloroform dissolves and moves into constant pressure funnel; There-necked flask is placed in 40 DEG C of water-baths, the chloroform soln of sulfo-diglycolyl chloride is instilled with the 1 second speed of 1.After dropping terminates, stirring reaction 3 hours at 140 DEG C.
The reactant liquor obtained is cooled to room temperature, in beaker, adds cold water, then the reaction solution of cooling is added in beaker, leave standstill with separatory funnel after fully stirring, make organic phase and aqueous phase separation.Add distilled water in organic phase after separation, after separatory funnel vibration, carry out being separated of organic phase and aqueous phase; The organic phase obtained is carried out twice separation with the hydrochloric acid solution of 1.0mol/L respectively, carries out twice separation, then carry out twice separation with 5wt% aqueous sodium carbonate with distilled water, last distilled water carries out repeatedly organic phase cleaning, until the pH=7 of aqueous phase after phase-splitting.Organic phase after cleaning moves in eggplant type flask, adds Na 2sO 4, stir and within two hours, make residual moisture in organic phase remove.
By the sodium sulphate elimination after crystallization, filtrate moves into eggplant type flask, and eggplant type flask removes solvent on the rotary evaporator, and with vacuum draw, by the removing of residual solution.For removing insoluble matter, use re-crystallizing in ethyl acetate 2 to 3 times; The productive rate being extracted agent product is 67%.
Characterize the extractant of preparation, result is as shown in Fig. 1 to Fig. 3.
Fig. 1 is N, the infrared spectrogram of N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide.Major absorbance peak is pointed out: at 2903cm -1the peak at place ,=the stretching vibration of the saturated c h bond of C-H is described, is in general methyl; 1496cm -1the peak at place, being produced by the stretching vibration of the C=C key entirety of phenyl ring, is aromatic skeleton vibration performance peak.At 770cm -1the peak at place, illustrates the out-of-plane bending vibration of aromatic ring=C-H.These two peaks exist simultaneously, show the aromatic having five adjacent hydrogen, i.e. the existence of monosubstituted benzene nucleus; 1664cm -1for carbonylic stretching vibration absworption peak, show that the deformation vibration of methyl and methylene absorbs; 1250cm -1for C-S-C asymmetric stretching vibration absworption peak.
Fig. 2 is N, and N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide is in deuterochloroform 1h-NMR composes, and the chemical shift of each proton is listed in table 2.3.In composition graphs 2.9, structure chart is known, and by the impact of other groups, the H in molecule can be divided into 4 classes, that is: 1 ,-N-CH 3on H; 3 ,-CH 2h on-S; 5, with the H that other groups are ortho position in phenyl ring; 6,7, with the H that other groups are non-ortho position in phenyl ring; Position 2,4 do not have H.Ratio according to the known various number of hydrogen atoms of integral curve in Fig. 2 .8 is 6:4:6:4, and the number of hydrogen atoms in hydrogen spectrum corresponding to each peak group and peak type indicate the symmetry of this molecule.
δH(400MHz,CDCl 3):3.232,3.298(6H,-CH 3-N)，3.406(4H，-CH 2-S-)，7.225-7.421(10H,-CH)。
Fig. 3 is N, N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide 13c NMR spectrogram, the 1-5 in table 1 represents the hydrogen in extractant structure chart corresponding to 1-5 carbon atom.76.761-77.396ppm what the peak at place was corresponding is the chemical shift of C in solvent carbon deuterium chloride; The signal (i.e. position 2) of two carbonyl carbon in the corresponding compound in peak at 169.208ppm place; 37.645ppm peak correspond to N-CH 3the chemical shift (i.e. position 1) of middle carbon, the peak at 33.817ppm place corresponds to S-CH 2the signal (i.e. position 3) of carbon, 127.093ppm, 128.203ppm, 129.914ppm are the chemical shift (i.e. position 4-7) of carbon in phenyl ring.
δC(400MHz，DMSO)：37.645(2C，CH 3-N-)，33.817(2C,-CH 2-S),127.415,127.740,129.864(2C,-CH)，169.208(2C，-C＝O)。
N, the structural formula of N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide is as follows:
Table 1N, the chemical shift of N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide proton hydrogen
The test of the equilibration time of embodiment 2 extractant extraction precious metal palladium.
Product prepared by embodiment 1 be dissolved in chloroform system, the concentration forming extractant is the chloroform soln of 0.02mol/L, and as organic phase, the aqueous solution of preparation palladium bichloride, the concentration making palladium is 50mg/L, as aqueous phase, implements extraction test.Wherein, organic phase and each 5mL of aqueous phase volume vibrate to extraction equilibrium in conical flask in water-bath constant temperature oscillator, controlling concentration of hydrochloric acid in extraction process is 3mol/L, amplitude is 160 ± 2spm, extraction temperature controls at 25 ± 0.5 DEG C, transfer to centrifugal phase-splitting in centrifuge tube after vibration terminates, the concentration of metal ions ICP-OES of the aqueous phase after phase-splitting measures.
Wherein,
Distribution coefficient D represents,
Extraction efficiency E (%) represents,
Reextraction efficiency E'(%) represent,
C oconcentration of metal ions in-starting aqueous solution
C iaqueous metal ion concentration after-extraction
C iaqueous metal ion concentration after '-strip
Under different extraction time, the extraction efficiency of Pd (II) is in table 2.
Under the different extraction time of table 2, extractant is to the extraction efficiency of Pd (II)
As can be seen from Table 2, the best extraction equilibrium time of Pd (II) is the best extraction efficiency of 90min, Pd (II) is 99.48%.
Embodiment 3 concentration of hydrochloric acid is on the test experiments of synthesis extractant extraction ability impact.
Extractant N prepared by embodiment 1, N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide is dissolved in chloroform system, and the concentration forming extractant is the chloroform soln of 0.02mol/L, as organic phase; The aqueous solution of preparation palladium bichloride, the concentration making palladium is 50mg/L, as aqueous phase, implements extraction test.Get in organic phase and each 5mL of aqueous phase volume and conical flask and vibrate in water-bath constant temperature oscillator to extraction equilibrium, amplitude is 160 ± 2spm, extraction temperature controls at 25 ± 0.5 DEG C, controlling concentration of hydrochloric acid in extraction process is 1 ~ mol/L, transfer to centrifugal phase-splitting in centrifuge tube after vibration terminates, after phase-splitting, the concentration of metal ions ICP-OES of aqueous phase measures.
After concussion enough time extraction equilibrium, under different concentration of hydrochloric acid to the extraction efficiency of Pd (II) in table 3.
Under the different concentration of hydrochloric acid of table 3, extractant is to the extraction efficiency of Pd (II)
As can be seen from Table 3, just 99.22% is reached to the extraction of Pd (II) under Low acid, afterwards along with the increase of concentration of hydrochloric acid remains unchanged substantially, to strong acid, there is stronger tolerance.
The test experiments that embodiment 4 aqueous phase hydrogen ion concentration affects extraction efficiency.
Extractant N prepared by embodiment 1, N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide is dissolved in chloroform system, and the concentration forming extractant is the chloroform soln of 0.02mol/L, as organic phase; The aqueous solution of preparation palladium bichloride, the concentration making palladium is 50mg/L, as aqueous phase, adds lithium chloride to keep aqueous phase chlorine ion concentration for 3mol/L, regulates H+ concentration to be respectively 1.36,1.63,2.12,2.46,2.82 and 3.23 and implements extraction test.Get in organic phase and each 5mL of aqueous phase volume and conical flask and vibrate in water-bath constant temperature oscillator to extraction equilibrium, amplitude is 160 ± 2spm, extraction temperature controls at 25 ± 0.5 DEG C, controlling concentration of hydrochloric acid in extraction process is 1 ~ mol/L, transfer to centrifugal phase-splitting in centrifuge tube after vibration terminates, after phase-splitting, the concentration of metal ions ICP-OES of aqueous phase measures.
After concussion enough time extraction equilibrium, under different aqueous phase hydrogen ion concentration to the extraction efficiency of Pd (II) in table 4.
The extractant synthesized under the different aqueous phase hydrogen ion concentration of table 4 is to the extraction efficiency of Pd (II)
The performance test experiment of extractant extraction different metal under the different concentration of hydrochloric acid condition of embodiment 5.
Extractant N prepared by embodiment 1, N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide is dissolved in chloroform system, the concentration forming extractant is the chloroform soln of 0.02mol/L, as organic phase, the aqueous solution obtaining metal soluble in water is as aqueous phase respectively for palladium bichloride, iron chloride, platinum chloride, zinc chloride, copper chloride, and the concentration of metal is all 50mg/L, implements extraction test.The volume ratio of aqueous phase and organic phase is 1:1, after the 90min that vibrates in water-bath constant temperature oscillator in organic phase and each 5mL of aqueous phase volume and conical flask reaches extraction equilibrium, amplitude is 160 ± 2spm, extraction temperature controls at 25 ± 0.5 DEG C, transfer to centrifugal phase-splitting in centrifuge tube after vibration terminates, after phase-splitting, the concentration of metal ions ICP-OES of aqueous phase measures.
Aqueous-phase concentration of hydrochloric acid is to N, N'-dimethyl-N, N'-diphenyl-3-sulphur glutaramide (DMDPhTDGA) impact on the extraction efficiency of extraction Pt (IV), Pd (II), Fe (III), Zn (II), Cu (II) is as shown in table 5.As can be seen from Table 5 when concentration of hydrochloric acid <4mol/L, the extraction yield of Pd (II) is very high, all be greater than 99.0%, but all very low <7.1% of extraction yield of other Pt (IV), Fe (III), Zn (II), Cu (II), but as concentration of hydrochloric acid >5mol/L, the extraction yield of Fe (III), Zn (II), Cu (II) rises a lot, is unfavorable for being separated Pd (II).Therefore, when being separated Pd (II) from the mixed solution honor of Pt (IV), Pd (II), Fe (III), Zn (II), Cu (II), concentration of hydrochloric acid <4mol/L should be kept.
Table 5DMDPhTDGA is on the impact of the extraction efficiency of extraction Pt (IV), Pd (II), Fe (III), Zn (II), Cu (II)
The test of embodiment 6 extractant extraction of palladium from mixed solution.
Extractant N prepared by embodiment 1, N '-dimethyl-N, N '-diphenyl-3-sulphur glutaramide is dissolved in chloroform system, the concentration forming extractant is the chloroform soln of 0.02mol/L, as organic phase, the aqueous solution obtaining metal soluble in water is as aqueous phase respectively for palladium bichloride, iron chloride, platinum chloride, zinc chloride, copper chloride, and the concentration of metal is all 50mg/L, implements extraction test.
First in the aqueous solution, adding NaOH, be NaOH concentration is 1mol/L, forms precipitation, with Filter paper filtering, by Fe (III), Zn (II), Cu (II) ion remaval in solution.The aqueous solution after filtration first adds hydrochloric acid solution and regulates pH=7, then adds hydrochloric acid and make the concentration of hydrochloric acid in the aqueous solution be 3mol/L.
By this aqueous solution and organic phase mixing, the volume ratio of aqueous phase and organic phase is 1:1, after the 90min that vibrates in water-bath constant temperature oscillator in organic phase and each 5mL of aqueous phase volume and conical flask reaches extraction equilibrium, amplitude is 160 ± 2spm, extraction temperature controls at 25 ± 0.5 DEG C, transfers to centrifugal phase-splitting in centrifuge tube after vibration terminates.After phase-splitting, the concentration of metal ions ICP-OES of aqueous phase measures.Extractant is respectively 3.2% to the extraction yield that Pd (II) extraction yield is 99.3%, Pt (IV).
The organic phase extracted is mixed with the hydrochloric acid solution of 0.1mol/L and strips.The volume ratio of aqueous phase and organic phase is 1:1, after the 90min that vibrates in water-bath constant temperature oscillator in organic phase and each 5mL of aqueous phase volume and conical flask reaches stripping equilibria, amplitude is 160 ± 2spm, and reextraction temperature controls at 25 ± 0.5 DEG C, transfers to centrifugal phase-splitting in centrifuge tube after vibration terminates.After phase-splitting, the concentration of metal ions ICP-OES of aqueous phase measures.The stripping rate of hydrochloric acid solution to Pd (II) of 0.1mol/L is 96.1%.

Claims (10)

1. a 3-sulphur glutaramide kind of extractants, is characterized in that, described extractant has following structural formula:
Wherein, R 1for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11; R 2for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11.
2. the preparation method of 3-sulphur glutaramide kind of extractants according to claim 1, is characterized in that, comprise the steps:
(1) 2, the preparation of 2 '-dimethly thiodiglycolate: 2,2 '-thiodiglycolic acid methyl alcohol is dissolved and obtains 2, the methanol solution of 2 '-thiodiglycolic acid, heat and remain on 5 ~ 100 DEG C, stir 3 ~ 15h, place and cool to room temperature, rotary evaporation removes methyl alcohol, then vacuum draw, remove residual methyl alcohol, obtain rough 2,2 '-dimethly thiodiglycolate;
(2) 2, the preparation of 2 '-3-sulphur glutaramide: prepare the chloroform soln of amine and the chloroform soln of the thick product of dimethly thiodiglycolate respectively, then the chloroform soln of thick for dimethly thiodiglycolate product is added drop-wise in the chloroform soln of amine, react at 20 ~ 100 DEG C, dropwise rear continuation and at 50 ~ 300 DEG C, react 2.5 ~ 8h reacted mixture is used HCl solution, Na successively 2cO 3solution and distilled water cyclic washing are extremely neutral, the organic layer Na obtained after phase-splitting 2sO 4drying, chloroform steaming removes with Rotary Evaporators by the filtrate after suction filtration, and then use re-crystallizing in ethyl acetate 2 ~ 3 times, obtain crystallized product, wherein, described amine has following structural formula:
Wherein, R 1for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11; R 2for aliphatic chain substituting group, the aliphatic cyclic substituting group of carbon number 4 ~ 10 or the aromatic substituents of carbon number 6 ~ 14 that carbon number 1 ~ 9 or carbon number are greater than 11.
3. preparation method according to claim 2, is characterized in that, in step (1), and 2, the molar ratio of material of 2 '-thiodiglycolic acid and methyl alcohol is 1:(2 ~ 3).
4. preparation method according to claim 2, is characterized in that, in step (2), and 2, the molar ratio of material of 2 '-dimethly thiodiglycolate and amine is 1:(2 ~ 3).
5. preparation method according to claim 2, is characterized in that, in step (2), the concentration of HCl solution is 0.1 ~ 5mol/L, Na 2cO 3the concentration of solution is 0.1 ~ 25wt%, HCl solution, Na 2cO 3the consumption of solution and distilled water is 1 ~ 1.5 times of the volume of mixture after reaction.
6. the application of 3-sulphur glutaramide kind of extractants according to claim 1 in extraction of palladium.
7. application according to claim 6, is characterized in that, comprises the steps: 3-sulphur glutaramide kind of extractants to be dissolved in organic solvent to be extracted liquid, under acid solution existent condition, with described extract to the aqueous solution containing palladium.
8. application according to claim 7, is characterized in that, described acid solution is hydrochloric acid, and the concentration of described hydrochloric acid is 1 ~ 9mol/L.
9.3-sulphur glutaramide kind of extractants comprises the application of the palladium in palladium, platinum, copper, iron and zinc ion mixed solution in extraction.
10. application according to claim 9, it is characterized in that, comprise the steps: 3-sulphur glutaramide kind of extractants to be dissolved in organic solvent to be extracted liquid, the mixed solution precipitation method containing palladium, platinum, copper, iron and zinc ion are removed copper, iron, zinc, obtain the mixed liquor containing palladium and platinum, then with above-mentioned extract, the mixed liquor containing palladium and platinum is extracted, the organic phase of separation is contacted with hydrochloric acid and strips, obtain the aqueous solution containing palladium.
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