CN1023406C - Synthesis of cross linked 2-ethyl pyridinyl polystyrene resin and its application - Google Patents
Synthesis of cross linked 2-ethyl pyridinyl polystyrene resin and its application Download PDFInfo
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- CN1023406C CN1023406C CN 87103759 CN87103759A CN1023406C CN 1023406 C CN1023406 C CN 1023406C CN 87103759 CN87103759 CN 87103759 CN 87103759 A CN87103759 A CN 87103759A CN 1023406 C CN1023406 C CN 1023406C
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Abstract
The present invention relates to the synthesis of resin having special performance and the application thereof to the separation and the concentration of noble metal mainly containing aurum. BPR resin has the following structure disclosed in the specification. The method for separating and concentrating noble metal mainly containing aurum with the BPR resin comprises: after being dissolved by royal water, materials containing the aurum are led in an exchange column loaded with the BPR resin, and the noble metal mainly containing the aurum is adsorbed on the resin; then, the noble metal is eluted down by the mixed liquor of hydrochloric acid and thiourea. The adsorption quantity of the BPR resin to the aurum is 520 mg/g(dry resin), and at the same time, the BPR resin also has certain adsorption capacity to palladium and platinum. Au can be quantitatively separated from an acidic solution containing a large number of metallic ions, such as cuprum ions, ferrum ions, cobalt ions, nickel ions, zinc ions, etc. The resin having special performance is suitable for the separation and the concentration of the aurum and the noble metal of aurum concentrate, electrolytic copper plants and samples of electronic elements containing the aurum.
Description
The invention belongs to a kind of synthetic method with resin of property.
For the synthetic method of the resin that is exclusively used in ADSORPTION OF GOLD, many reports were arranged, for example Vernon on the document
[1] [2]Synthesized the hydroxyl oxime resin Deng the people, in order to the gold of absorption in the acidic medium, its result is because relatively poor and be not applied to the selectivity of gold.
Myasoedova
(3)Once synthesized the resin that contains the pyrazoles functional group Deng the people, and be used for SEPARATION ENRICHMENT OF GOLD WITH, but found as lot of F e(III), the Cu(II) with the Au(IV) during coexistence, the suction gold amount of this resin descends significantly.
Purpose of the present invention, be synthetic a kind of strong to golden selectivity, adsorptive capacity big, the easy resin of wash-out.
In order to achieve the above object, we adopt organometallic compound and the effect of chloromethylated polystyrene resin, carry out the linked reaction of C-C, the effective functional group-ethylpyridine in effective extraction agent of gold, import on the polystyrene resin skeleton, synthesized the crosslinked α-ethyl pyridinyl polystyrene resin that gold is had special sorption property, be called for short the BPR resin, structure is:
Its synthetic route has two:
(1) by Grignard reagent synthetic (I method):
At first use chloromethyl ether under Zinc Chloride Anhydrous catalysis, chloromethyl is introduced on the polystyrene resin skeleton.In addition, with monobromethane and magnesium chips reaction, make ethylmagnesium bromide.With the α-Jia Jibiding effect, convert the α-Jia Jibiding magnesium bromide to again.With α-Jia Jibiding magnesium bromide and chloromethyl polystyrene resin reaction, just obtain the BPR resin.
(2) by organo-metallic sodium reagent synthetic (II method)
At first, obtain α-Jia Jibiding sodium with sodium Metal 99.5 and α-Jia Jibiding reaction.With the chloromethyl polystyrene resin reaction, just make the BPR resin again.
With synthetic resin of the present invention, in the various mineral acid systems and the acidity scope from weak acid to strong acid of gold, gold all there is the good adsorption effect, adsorptive capacity 520mg/g(dried resin).
Simultaneously, platinum, palladium also there is certain adsorptive power.Selectivity is strong, can be from the acidic solution that contains metal ions such as a large amount of copper, iron, cobalt, nickel, zinc Quantitative Separation go out the Au(III).Temperature influence is little, inhales golden efficient all more than 98% in 20 ℃-80 ℃.The easy wash-out of resin.It is the comparatively ideal resin that reclaims gold in gold concentrate, electrolysis copper work, military project, the civil electronic element gold contained matter sample.
Example 1 usefulness I method is synthesized the BPR resin
14.4 gram chloromethyl polystyrene resins are put into 40 milliliters of benzene, place a few hours, until pearl body swelling.
Electronic stirring, thermometer, constant pressure funnel, reflux condensing tube are installed on 500 milliliters of four-hole bottles.Connect a bubbler and a calcium chloride drying tower again successively on the prolong top.
In reaction flask, add 4.6 gram magnesium chips and micro iodine earlier, add 15 milliliters of mixed solutions again, start stirring by 20.8 gram monobromethanes and 120 milliliters of n-butyl ethers.It is initial to be swift in response, keeping reactant seethes with excitement slightly, drip the monobromethane and the n-butyl ether mixed solution of residue, dropwised in 30 minutes, refluxed 1 hour, magnesium chips is reacted completely as far as possible, be warming up to 120 ℃-130 ℃ then, keep this temperature, drip mixed solution, in 30 minutes, dropwise by 17.8 gram α-Jia Jibidings and 40 milliliters of n-butyl ethers.Be cooled to 70 ℃-80 ℃, add use the benzene swelling in advance chloromethyl polystyrene resin, kept this thermotonus 8 hours.Be cooled to room temperature.With ammonium chloride and mixture of ice and water hydrolysis, soak a few hours with 10% hydrochloric acid soln again, take out disacidify liquid, water is given a baby a bath on the third day after its birth time again, takes out with the suction filtration rod and anhydrates, must red pearl body.This red pearl body is placed the Sha Shi extractor, use extraction using alcohol 5 hours, extremely effusive extract is till the water white transparency, obtains orange red pearl body, airing, and sieve goes to broken end, gets the dried BPR resin of 4.1 grams.
Example 2
Experimental installation and monomer consumption are same as example 1.Reflux after 1 hour, be warming up to 110 ℃-120 ℃, keep this temperature, drip the mixed solution by 17.8 gram α-Jia Jibidings and 40 milliliters of n-butyl ethers, dropwised in 30 minutes, be cooled to 60 ℃-70 ℃, all the other are operated with example 1.Obtain 2.6 grams and do the BPR resin.
Example 3
Experimental installation and unit consumption are same as example 1.Refluxed 1 hour, and be warming up to 130 ℃-140 ℃, keep this temperature, drip the mixed solution by 17.8 gram α-Jia Jibidings and 40 milliliters of n-butyl ethers, dropwised in 30 minutes, be cooled to 80 ℃-90, all the other are operated with example 1.Obtain 3.7 grams and do the BPR resin.
Example 4 usefulness II methods are synthesized the BPR resin
On 10 liters four-hole bottle, electric mixer is installed, thermometer, nitrogen protection device, spherical reflux condensing tube, and connect a bubbler and a calcium chloride drying tower successively on the prolong top.
The sodium Metal 99.5 of 3500 milliliters of α-Jia Jibidings and the new chopping of 190 grams is added in the reaction flask, feed nitrogen, start stirring, be warming up to 100 ℃, keep this temperature up to the sodium Metal 99.5 complete reaction.Be cooled to 55 ℃-60 ℃ then, open reaction flask, add the chloromethyl polystyrene resin that 700 grams are done rapidly.Refilled instrument, still under nitrogen protection, 45 ℃ of holding temperatures slowly stirred 8-9 hour.
With the careful hydrolysis of 1200 gram frozen water, temperature is no more than 50 ℃, takes out the mixed solution that anhydrates after separating with the suction filtration rod, washes resin with water to pH ∽ 8, with 800 milliliters of 1: 1 salt acid soak, then, take out disacidify liquid, wash with water to pH ∽ 4, from reaction flask, take out resin, with ethanol continuous extraction 8 hours, airing, obtain the orange red pearl body of 1438 grams.
Example 5
Experimental installation and monomer consumption are same as example 4.Feed nitrogen, start stirring and be warming up to 90 ℃, keep this temperature until the sodium Metal 99.5 complete reaction.Be cooled to 60 ℃ then.Open reaction flask, add the chloromethyl polystyrene resin that 700 grams are done rapidly, refilled instrument, still under nitrogen protection, 50 ℃ of holding temperatures.All the other operations are same as example 4.Get 1240 gram pearl bodies.
Example 6
Experimental installation and monomer consumption are same as example 4.Feed nitrogen, start stirring and be warming up to 120 ℃, keep this temperature, until the sodium Metal 99.5 complete reaction.Be cooled to 60 ℃ then.Open reaction flask, add the chloromethyl polystyrene resin that 700 grams are done rapidly, refilled instrument, still under nitrogen protection, 55 ℃ of holding temperatures.All the other operations are same as example 4.Get 1406 gram pearl bodies.
Claims (7)
1, a kind of structure is
The synthetic method of crosslinked α-ethyl pyridinyl polystyrene resin (BPR resin), it is characterized in that it makes by Grignard reagent or organo-metallic sodium reagent and chloromethyl polystyrene resin effect:
(1) by Grignard reagent synthetic (I method)
At first use chloromethyl ether under Zinc Chloride Anhydrous catalysis, chloromethyl is introduced on the polystyrene resin skeleton, make chloromethyl polystyrene resin; In addition,, make ethylmagnesium bromide, with the α-Jia Jibiding effect, convert the α-Jia Jibiding magnesium bromide to again,, promptly make the BPR resin α-Jia Jibiding magnesium bromide and chloromethyl polystyrene resin reaction with monobromethane and magnesium chips reaction;
(2) by organo-metallic sodium reagent synthetic (II method)
At first, obtain α-Jia Jibiding sodium, with the chloromethyl polystyrene resin reaction, just make the BPR resin again sodium Metal 99.5 and α-Jia Jibiding reaction.
2, according to the described BPR resin of claim (1) synthetic method, it is characterized in that when synthesizing with monobromethane and magnesium chips reaction, the ethylmagnesium bromide and the α-Jia Jibiding that make are done the time spent by Grignard reagent, temperature is 120 ℃-130 ℃; The α-Jia Jibiding magnesium bromide and the chloromethyl polystyrene resin that make are done the time spent, and temperature is 70 ℃-80 ℃.
3, according to the described BPR resin of claim (1) synthetic method, it is characterized in that when synthesizing with monobromethane and magnesium chips reaction, the ethylmagnesium bromide and the α-Jia Jibiding that make are done the time spent by Grignard reagent, temperature is 110 ℃-120 ℃; The α-Jia Jibiding magnesium bromide and the chloromethyl polystyrene resin that make are done the time spent, and temperature is 60 ℃-70 ℃.
4, according to the described BPR resin of claim (1) synthetic method, it is characterized in that when synthesizing with monobromethane and magnesium chips reaction, the ethylmagnesium bromide and the α-Jia Jibiding that make are done the time spent by Grignard reagent, temperature is 130 ℃-140 ℃; Smelling of the α-Jia Jibiding magnesium and the chloromethyl polystyrene resin that make are done the time spent, and temperature is 80 ℃-90 ℃.
5,, it is characterized in that the temperature of reaction of sodium Metal 99.5 and α-Jia Jibiding is 100 ℃ when synthesizing by the organo-metallic sodium reagent according to the described BPR resin of claim (1) synthetic method; The temperature of reaction of α-Jia Jibiding sodium and chloromethyl polystyrene resin is 45 ℃.
6,, it is characterized in that the temperature of reaction of sodium Metal 99.5 and α-Jia Jibiding is 90 ℃ when synthesizing by the organo-metallic sodium reagent according to the described BPR resin of claim (1) synthetic method; The temperature of reaction of α-Jia Jibiding sodium and chloromethyl polystyrene resin is 50 ℃.
7,, it is characterized in that the temperature of reaction of sodium Metal 99.5 and α-Jia Jibiding is 120 ℃ when synthesizing by the organo-metallic sodium reagent according to the described BPR resin of claim (1) synthetic method; The temperature of reaction of α-Jia Jibiding sodium and chloromethyl polystyrene resin is 55 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103759 CN1023406C (en) | 1987-05-22 | 1987-05-22 | Synthesis of cross linked 2-ethyl pyridinyl polystyrene resin and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103759 CN1023406C (en) | 1987-05-22 | 1987-05-22 | Synthesis of cross linked 2-ethyl pyridinyl polystyrene resin and its application |
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| Publication Number | Publication Date |
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| CN87103759A CN87103759A (en) | 1988-12-07 |
| CN1023406C true CN1023406C (en) | 1994-01-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 87103759 Expired - Fee Related CN1023406C (en) | 1987-05-22 | 1987-05-22 | Synthesis of cross linked 2-ethyl pyridinyl polystyrene resin and its application |
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| CN101279292B (en) * | 2008-05-06 | 2010-04-14 | 杭州师范大学 | Catalyst for hydrosilylation of olefins containing fluorine and preparation |
| CN102399342B (en) * | 2011-10-09 | 2014-04-02 | 山东省科学院能源研究所 | Surface functionalization method of poly (styrene-divinylbenzene) microspheres |
| CN108704668A (en) * | 2018-06-13 | 2018-10-26 | 福州华博立乐新材料科技有限公司 | A kind of catalyst for synthesizing 7- chloro-2-oxoheptanoates |
| CN115845807B (en) * | 2022-11-29 | 2024-05-07 | 西安交通大学 | Adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid and preparation method and application thereof |
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