阅读说明：本技术 用聚苯乙烯-苯并恶唑硫醚树脂分离提取钯的方法 (Method for separating and extracting palladium by using polystyrene-benzoxazole thioether resin ) 是由 黄章杰 蒋绍松 邵敏 金次 陈慕涵 叶群 范梅 罗国婷 于 2019-10-21 设计创作，主要内容包括：用聚苯乙烯-苯并恶唑硫醚树脂分离提取钯的方法,属于铂族金属的提取方法。本发明以聚苯乙烯-苯并恶唑硫醚树脂(简称PS-BOS)为吸附剂,按固液比1:100(g/mL)吸附0.1～0.2 mol/L盐酸介质中的Pd(II),PS-BOS将Pd、Pt、Rh、Cu、Ni、Fe、Zn混合溶液中的Pd吸附,而将Pt、Rh、Cu、Ni、Fe、Zn保留在水相,用0.1～0.4mol/L硫脲溶液解吸树脂上的Pd。本发明吸附剂差异化吸附Pd、Pt、Rh、Cu、Ni、Fe、Zn,分离Pd与Pt、Rh、Cu、Ni、Fe、Zn,且Pd与Pt、Pd与Rh、Pd与Cu、Pd与Ni、Pd与Fe、Pd与Zn分离系数均大于10<Sup>4</Sup>,Pd回收率高于97.0%。该吸附剂稳定性好,可重复使用,操作流程简单,环境友好。(A method for separating and extracting palladium by using polystyrene-benzoxazole thioether resin belongs to a method for extracting platinum group metals. The invention takes polystyrene-benzoxazole thioether resin (PS-BOS for short) as an adsorbent, Pd (II) in a hydrochloric acid medium is adsorbed by the PS-BOS according to the solid-to-liquid ratio of 1:100(g/mL) and 0.1-0.2 mol/L, the Pd in a mixed solution of Pd, Pt, Rh, Cu, Ni, Fe and Zn is adsorbed by the PS-BOS, the Pt, Rh, Cu, Ni, Fe and Zn are retained in a water phase, and the Pd on the resin is desorbed by a thiourea solution of 0.1-0.4 mol/L. The adsorbent of the invention differentially adsorbs Pd, Pt, Rh, Cu, Ni, Fe and Zn, separates Pd from Pt, Rh, Cu, Ni, Fe and Zn, and has separation coefficients of Pd and Pt, Pd and Rh, Pd and Cu, Pd and Ni, Pd and Fe, Pd and Zn which are all larger than 10 4 and the recovery rate of Pd is higher than 97.0 percent. The adsorbent has the advantages of good stability, repeated use, simple operation process and environmental protection.)

1. The method for separating and extracting palladium by using the polystyrene-benzoxazole thioether resin is characterized by comprising the following steps: polystyrene-benzoxazole thioether resin (PS-BOS for short) is used as an adsorbent, Pd, Pt, Rh, Cu, Ni, Fe and Zn are adsorbed according to a solid-to-liquid ratio of 1:100(g/mL), and a medium is H⁺Pd (II) in the mixed solution with the concentration of 0.1-0.2 mol/L, wherein the structural formula of PS-BOS is as follows:

2. The method according to claim 1, characterized by comprising the steps of:

(1) Preparing a water phase: h of the mixed solution of Pd, Pt, Rh, Cu, Ni, Fe and Zn is adjusted by HCl⁺Concentration of H in the mixed solution⁺At a concentration of 0.1～0.2mol/L；

(2) Adding PS-BOS with a certain mass into a mixed solution containing Pd, Pt, Rh, Cu, Ni, Fe and Zn according to a solid-to-liquid ratio of 1:100(g/mL), stirring for 10-30 min, and filtering out the PS-BOS loaded with Pd;

(3) taking the PS-BOS loaded with Pd adsorbed in the step (2), stirring or oscillating for 10-20 min by using 0.1-0.4 mol/L thiourea solution according to the solid-to-liquid ratio of 1:50(g/mL), and desorbing Pd on the PS-BOS;

(4) And (4) taking the PS-BOS desorbed in the step (3), washing the PS-BOS with distilled water for 2 times, returning to the step (2), and adsorbing the Pd, Pt, Rh, Cu, Ni, Fe and Zn mixed solution again to realize the reutilization of the PS-BOS.

3. The method of claim 2, wherein: in the step (2), the concentration of Pd in the mixed solution of Pd, Pt, Rh, Cu, Ni, Fe and Zn is 10-500 mg/L, the concentration of Pt is 15-450 mg/L, the concentration of Rh is 14-400 mg/L, the concentration of Cu is 25-600 mg/L, the concentration of Ni is 32-550 mg/L, the concentration of Fe is 18-650 mg/L, and the concentration of Zn is 28-700 mg/L.

4. the method of claim 2, wherein: and (2) further measuring the concentrations of Pd, Pt, Rh, Cu, Ni, Fe and Zn in the water phase, calculating the amounts of Pd, Pt, Rh, Cu, Ni, Fe and Zn adsorbed by the PS-BOS by a subtraction method, and calculating the separation coefficients of Pd and Pt, Pd and Rh, Pd and Cu, Pd and Ni, Pd and Fe and Pd and Zn.

5. The method according to claim 2, wherein the step (3) is further to determine the concentration of Pd in the desorption solution and calculate the recovery rate of Pd.

Technical Field

The present invention belongs to a method for extracting platinum group metals, particularly to a method for separating palladium from mixed metal ion solution by using heterocyclic polystyrene resin.

background

The adsorption method is applied to the separation and extraction of precious metals from the 70 th century, and through continuous research for decades, only activated carbon is used for adsorbing gold in alkaline cyanide solution to realize large-scale application, the adsorption method is used for extracting platinum group metals in platinum-palladium flotation concentrate or platinum group metal secondary resource chlorination leachate, precious base separation is firstly carried out before single platinum group metal extraction, the separation process is long, the recovery rate is low, and the method is still in the laboratory exploration stage so far, and the main problems faced by the adsorption method are lack of an adsorbent with good stability, high selectivity and large adsorption capacity. The development of a novel adsorbent which has high selectivity, few separation steps and strong adaptability and can be repeatedly used for efficiently separating and extracting the platinum group metals in the chlorination leaching solution is a key problem which is urgently needed to be solved by the current platinum group metal metallurgy. In recent years, some adsorbents using polystyrene resin as a matrix have attracted more and more attention in the field of separation and extraction of platinum group metals due to the unique chemical functional groups and high chemical stability, among which thiazole polystyrene resin has been used for separation and extraction of iridium and platinum in a chlorination medium. The inventor of the present application provides a method for separating iridium and platinum by adsorbing and separating iridium and platinum in a hydrochloric acid medium by using polystyrene-4-methylthiazole sulfoxide resin (Chinese patent ZL 201610575597.1), but the inventor needs to further explore the application of other heterocyclic polystyrene resin in platinum group metal adsorption and separation.

Disclosure of Invention

aiming at the technical problem of the metallurgical industry that the adsorption method is used for efficiently separating and extracting palladium in chloridized leachate of platinum group metal resources, the invention aims to provide a method for preparing a catalyst by using polystyrene-benzoxazole thioether resin (PS-BOS for short)AsThe adsorbent is a method for directly adsorbing and separating Pd from a mixed solution of Pd, Pt, Rh, Cu, Ni, Fe and Zn in a high-selectivity one-step manner without noble-base separation, and the PS-BOS adsorbent is divided intoHigh separation efficiency and good stability, shortens the process of palladium extraction and separation, and has obvious practical value.

The invention is completed by the following technical scheme: the method for separating and extracting palladium by using the polystyrene-benzoxazole thioether resin is characterized by comprising the following steps: polystyrene-benzoxazole thioether resin (PS-BOS for short) is used as an adsorbent, Pd, Pt, Rh, Cu, Ni, Fe and Zn are adsorbed according to a solid-to-liquid ratio of 1:100(g/mL), and a medium is H⁺Pd (II) in the mixed solution with the concentration of 0.1-0.2 mol/L, wherein the structural formula of PS-BOS is as follows:

Further, the steps of the technical scheme comprise the following steps:

(1) Preparing a water phase: h of the mixed solution of Pd, Pt, Rh, Cu, Ni, Fe and Zn is adjusted by HCl⁺Concentration of H in the mixed solution⁺The concentration is 0.1-0.2 mol/L;

(2) Adding PS-BOS with a certain mass into a mixed solution containing Pd, Pt, Rh, Cu, Ni, Fe and Zn according to a solid-to-liquid ratio of 1:100(g/mL), stirring for 10-30 min, and filtering out the PS-BOS loaded with Pd;

(3) Taking the PS-BOS loaded with Pd adsorbed in the step (2), stirring or oscillating for 10-20 min by using 0.1-0.4 mol/L thiourea solution according to the solid-to-liquid ratio of 1:50(g/mL), and desorbing Pd on the PS-BOS;

(4) And (4) taking the PS-BOS desorbed in the step (3), washing the PS-BOS with distilled water for 2 times, returning to the step (2), and adsorbing the Pd, Pt, Rh, Cu, Ni, Fe and Zn mixed solution again to realize the reutilization of the PS-BOS.

The step (2) is as follows: the concentration of Pd in the mixed solution of Pd, Pt, Rh, Cu, Ni, Fe and Zn is 10-500 mg/L, the concentration of Pt is 15-450 mg/L, the concentration of Rh is 14-400 mg/L, the concentration of Cu is 25-600 mg/L, the concentration of Ni is 32-550 mg/L, the concentration of Fe is 18-650 mg/L, and the concentration of Zn is 28-700 mg/L.

The step (2) is further as follows: the concentrations of Pd, Pt, Rh, Cu, Ni, Fe and Zn in the water phase are measured, the amount of Pd, Pt, Rh, Cu, Ni, Fe and Zn adsorbed on the PS-BOS is obtained by a subtraction method, and the separation coefficients of Pd and Pt, Pd and Rh, Pd and Cu, Pd and Ni, Pd and Fe and Pd and Zn are calculated.

The step (3) is further as follows: and (3) determining the concentration of Pd in the desorption solution, and calculating the recovery rate of Pd extracted from PS-BOS.

The invention has the beneficial effects that: the wet process route for treating platinum group metal resources by the chlorination method is perfected, the environment is protected, the extraction period is shortened, the production cost is reduced, and the method conforms to the principles of energy conservation, emission reduction and sustainable development of mining and metallurgy industries. The separation coefficients of Pd and Pt, Pd and Rh, Pd and Cu, Pd and Ni, Pd and Fe, Pd and Zn are all more than 10⁴The high-selectivity one-step separation of Pd from Pt, Rh, Cu, Ni, Fe and Zn is realized, and the PS-BOS adsorbent has good stability and can be repeatedly used.

The above advantages can be seen from the experiment, the adsorption experiment result of palladium is as follows:

Weighing 1.0g of PS-BOS as a stationary phase, adding into a Pd (II) solution with the concentration of 10.0g/L and the concentration of 0.1mol/L of C (HCl), oscillating for 30min, and filtering out PS-BOS loaded with Pd (II); the Pd adsorption amount was measured by adding the PS-BOS having Pd (II) supported thereon, which had been filtered off, to 50mL of a 0.4mol/L thiourea solution, shaking for 20min, filtering off the PS-BOS in the desorption solution, washing the PS-BOS with distilled water 2 times, and adsorbing the same Pd (II) solution again, and the results of measuring the maximum static adsorption capacity for 5 cycles are shown in Table 1:

TABLE 1 determination of maximum static adsorption Capacity of the cycles

Number of cycles	1	2	3	4	5
						maximum static adsorption Capacity (mg/g)	221.8	221.2	220.7	220.2	219.6

As can be seen from Table 1, after 5 times of cyclic use, the maximum static adsorption capacity of PS-BOS to Pd (II) is not obviously reduced, the adsorption capacity of PS-BOS is large, the stability is good, and the PS-BOS can be cyclically used for many times.

The process of the present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

Detailed Description

method for separating Pd in mixed metal ion solution and effect thereof