CN1005820B

CN1005820B - Resin for separating and gathering valuable metal

Info

Publication number: CN1005820B
Application number: CN86103557.7A
Authority: CN
Inventors: ***; 陈伟朱; 林雪; 李玲颖; 何炳林
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 1986-05-26
Filing date: 1986-05-26
Publication date: 1989-11-22
Also published as: CN86103557A

Abstract

The present invention relates to a method for synthesizing AP resin with special performance, and application of the AP resin. The structure of the AP resin is disclosed in the specification; the AP resin can be used for separating and enriching gold in gold containing minerals and gold (palladium or platinum) containing salt solutions. The method of the present invention comprises the following steps: the gold (palladium or platinum) of gold containing materials is adsorbed on the AP resin by an adsorbing column which is filled with the AP resin, and then, different elution solutions are used for separating and enriching the gold, the palladium and the platinum. The absorption capacity of the AP resin for the gold reaches 500 to 600 milligrams / gram resin, but most of base metals can not be adsorbed basically.

Description

Use chelating to set to separate, the method for enriching precious metal

The present invention relates to the synthetic of a kind of resin (AP resin) with property and from various contain gold mineral and contain gold (or palladium, the platinum) solution separate, the method for enrichment gold (or palladium, platinum).

About using the problem of various resin sorption gold, the various countries scholar once did many work, for example at Brit.Patent 1,153,717(1969) once mentioned the method that reclaims gold with the isothiourea resin; Japan special permission 56-20132(1981) once mentioned with thiol resin and come the sorption gold, but the stability of this class thioretinite is not good, and be difficult to wash-out, therefore never obtain practical application by the gold of sorption; People such as Myasoedova had once synthesized the resin concentration precious metal (1) that contains the pyrazoles functional group, but at lot of F a ³⁺When existing, this resinoid seriously reduces the sorption amount of gold.In addition, F.Varnon also once did the test (2) of hydroxamic acid resin sorption gold, but above-mentioned various resin is not ideal to the sorptive power and the eluting power of gold.

An object of the present invention is to develop a kind of resin, it can from gold mine, contain the catalyst of gold (or palladium, platinum) and contain the various solution of gold (or palladium, platinum) and waste liquid reclaim gold (or palladium, platinum), and can be in the presence of a large amount of association ions (as iron, cobalt, copper, nickel plasma) sorption gold (or palladium, platinum) optionally; Another object of the present invention is to seek the method that gold and other noble metals are analyzed in a kind of separation, Fu Ji And quantitatively.

In order to achieve the above object, we have synthesized a kind of chelating resin-AP resin, and this resin is to Au ³⁺Ability height (palladium, platinum are also had certain sorptive power), and to other common coexistent metallic ion not sorptions substantially, therefore utilizing the AP resin is available separation, enrichment and purifying gold (or palladium, platinum), its whole exchange process is as follows: the material that contains gold (or palladium, platinum) with aqua regia dissolution after, from top to bottom by the adsorption column of AP resin is housed, then gold (or palladium, platinum) and some other base metal all by sorption on the AP resin, earlier with HCl eluant solution base metal, use HCl-NaClO more then ₄Solution elutes noble metal wash-outs such as palladium, platinum to gold with acetone one hydrochloric acid solution at last, perhaps the resin calcination that only contains gold (or palladium, platinum), then can obtain highly purified gold (or palladium, platinum).For synthetic AP resin, can be styrene and two (methacrylic acid) glycol ester (or divinylbenzene) copolymerzation with cross-linking spheroiding EVAs, carry out the EVA that Friedel-crafts reaction promptly obtains its chloromethylation with chloromethyl ether then, the latter and α-An Jibiding reaction then obtain the AP resin.

Its sorption capacity is up to 500-600 milligram/gram resin when using AP resin sorption gold.And this resin for platinum, palladium also have certain sorptive power, but to the not sorption basically of most base metals, so noble metal is had higher selectivity.Simultaneously can adopt different leacheates that gold-palladium, gold-platinum or the palladium-platinum ion of sorption on the AP resin eluted from post respectively, to reach the purpose of separation.Noble metal is worth expensive, can extract gold (or other noble metals) with method of the present invention from ore, industrial wastewater or seawater, thereby have very high economic worth.

For implementing method of the present invention is described, now be exemplified below:

Example 1:

30 gram styrene, 2 gram methacrylate glycol esters (EGDM), 40 gram n-butyl ethers, 0.4 gram benzoyl peroxide are joined after mixing in the there-necked flask that fills 240ml water and 2.4 gram gelatin; in 80 ℃ of following polymerizations 4 hours; after keeping 4 hours under 90 ℃; remove n-butyl ether with steam distillation; air-dry back sieve is got the bead (copolymer worker) of 0.2-0.8mm, and the receipts amount is 28 grams.

Example 2:

With 40 gram styrene, 5 gram methacrylate glycol esters, all the other steps can obtain bead (copolymer I) 42 grams of 0.2-0.8mm with example 1.

Example 3:

With the experimental implementation of 50 gram styrene and 8 gram methacrylate glycol esters repetition examples 1, obtain bead 49 grams of copolymer I.

Example 4:

The above-mentioned copolymer I that makes of 30 grams is joined in the there-necked flask, add 200 gram chloromethyl ethers, 15 gram zinc dichloride, reaction is 14 hours under 38 ℃, and obtaining chlorinty is the chloromethylation EVA (copolymers II) of 14-21%.

Example 5:

4 gram chloromethylation EVAs are put into the there-necked flask of 100ml, add 2 gram α-An Jibiding and 20ml dimethyl formamides, in 60 ℃ of reactions 6 hours down, product obtains having the AP resin of the following chemical structure with acetone and water washing:

The output of resin is 11 grams.

Example 6:

Experiment with 4 gram α-An Jibidings repetition examples 5 obtains AP resin 13 grams.

Example 7:

Experiment with 6 gram α-An Jibidings repetition examples 5 obtains AP resin 15.

Example 8:

Take by weighing the AP resin that 30 milligrams of methods of using make, adding 20ml concentration is the gold solution of 1 mg/ml, soaks 24 hours, and And swayed under 35 ℃ temperature 2 hours, and recording its sorption amount is 609 milligrams/gram resin.

Example 9:

Replace EGDM to make the synthetic AP resin (method is with example 1,2,3) of crosslinking agent with divinylbenzene (DVB), the gained resin is 541 a milligrams/gram resin to the sorption amount of gold.

Example 10:

In the colorimetric cylinder of 25ml, adding 0.1 gram AP resin and 1ml concentration are that the goldstandard solution ， And of 100 μ g/ml is diluted to 10ml with 2NHCl, under 25 ℃ with the electric agitator different time that vibrates, get the solution 2ml after the vibration, measure absorbance, the results are shown in Table 1 with the crystal violet method.

By table 1 as seen in 2.5 minutes, the Au(II) promptly all by sorption.

Example 11:

Method is with example 10, but is diluted to different acidity, and duration of oscillation all kept 5 minutes, the results are shown in Table 2.Its explanation HCl concentration is in the scope of 0.1-8N, and resin all can quantitative sorption gold.

Table 2, concentration of hydrochloric acid are to the influence of resin sorption gold

Example 12:

Take by weighing 1 gram AP resin in the colorimetric cylinder of 25ml, add the Ti(IV), the V(V), the MO(VI), Cd ²⁺, Fe ²⁺, the Sb(III), the Fe(III), Al ³⁺, the Tl(III), the Cr(III), Sc ³⁺, La ³⁺, Mg ²⁺, Ca ²⁺, Mn ²⁺, CO ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺, Hg ²⁺, Pb ²⁺, Sn ²⁺Each 1mg of plasma was diluted to 25ml with 1NHCl and rare chloroazotic acid (1: 1) respectively, 25 ℃ of following constant temperature vibrations 1 hour.Get 5ml solution and steam, add the 50mg powdered carbon, evaporate to dryness to about 2ml.Do semiquantitative spectral analysis, with the standard sample comparison without the resin sorption, it the results are shown in Table 3.

Example 13:

In 0.1 gram AP resin, add the Os(IV), the Ir(IV), the Pt(IV), the Ru(III), the Rh(III), the Pd(II) each 20 μ g of standard liquid, be diluted to 10ml with variable concentrations hydrochloric acid respectively again.Vibration is 1 hour under 25 ℃ of constant temperature.Make the spectrum sample and take the photograph spectrum with example 12, it the results are shown in table 4.Use same method, get 100 μ g Ag ₂SO ₄, use 1M H ₂SO ₄Repeat above-mentioned test as medium, resin is to Ag as a result ⁺Not sorption.But when using rare HCl and rare chloroazotic acid medium behind the AP resin dress post, Pt and Pd all can be quantitatively by sorptions.

Example 14:

Earlier the solution of palladium and platinum by containing the chromatographic column of AP resin, then with the HCl-NaClO of variable concentrations ₄Be leacheate, measure the Pd(II respectively), the Pt(IV) the rate of recovery, it the results are shown in Table 5 and table 6.With repeating above-mentioned test with gold solution, find that gold can not be by HCl-NaClO with method ₄Wash-out.

Can find out wash-out Pd(II from table 5, table 6) best leacheate be 2N HCl-0.15-0.5NNaClO ₄, and wash-out Pt(IV) best leacheate be 3～5N HCl-0.6N NaClO ₄

Example 15:

In the volumetric flask of two 500ml, respectively add a certain amount of goldstandard solution and dense HCl84 milliliter, be diluted to scale (this moment, the concentration of acid was 2N) with running water, shake up, cross post respectively, wash pillar to remove interfering ion, at last with 90% acetone-5%HCl wash-out gold with 1N HCl then.For in the enrichment and the recovery of underwater gold from the beginning, it the results are shown in Table 6, for the enrichment of lake underwater gold, should add a little dense HCl earlier, stirs the back and adds a spot of solid-state KMnO ₄, be the micro mist redness and do not take off after making its dissolving.Add a small amount of dense HCl again and make KMnO ₄Fade, its filtrate is crossed post, the results are shown in Table 8.

From example 14 and 15 as can be known, contain gold mineral and salt solution, can use HCl-NaClO earlier what contain platinum, palladium and gold simultaneously ₄Eluant solution platinum and palladium are used 90% acetone-5%HCl eluant solution gold again.

Example 16:

(wherein contain NaCl0.5M, MgSO with running water preparation 1000ml simulated seawater earlier ₄0.05M, CaCl ₂5g, KCl0.35g, Al ³⁺0.1g, Cr ³⁺1mg, Ni4mg, Fe ³⁺0.5mg, the V(V) 1mg, Pb ²⁺100 μ g), do the sorption test with the AP resin then, the results are shown in Table 9.

List of references

〔1〕G.V.Myasoedova.et′al，Talanta，23（1976）866-868。

〔2〕F.Vernon，et′al，Anal.Chim.Acta 123（1981）309-313。

Claims

1, the chelating resin of a kind of use with (III) structure separates, enrichment contains gold mineral, contain the method for the gold in the golden salting liquid, it is characterized in that it is the adsorption column of gold-containing solution by filling with chelating resin, use leacheate golden wash-out then, with separation, enrichment gold.

2, contain gold mineral, contain method golden in the golden salting liquid according to the said separation and concentration of claim 1, it is characterized in that what its drip washing operation was performed such: wash post with HCl solution earlier and remove base metal, use HCl-NaClO then ₄Acetone-HCl eluant solution gold is used in solution drip washing (if also containing palladium and platinum in the material to be processed except that containing gold) at last.

3, contain gold mineral, contain method golden in the golden salting liquid according to the said separation of claim 2, enrichment, it is characterized in that the concentration of HCl solution used in the drip washing operation is 1N, the HCl-NaClO of drip washing palladium ₄The concentration proportioning of solution is 2NHCl-0.15～0.5N NaClO ₄, the best proportioning of wash-out platinum is 3～5NHCl-0.6NNaClO ₄, and the most handy 90% acetone of the leacheate-5%HCl solution of wash-out gold.