阅读说明：本技术 一种低温捕集回收废催化剂中铂族金属的方法 (Method for low-temperature trapping and recovering platinum group metal in waste catalyst ) 是由 郭宇峰 王帅 杨凌志 陈凤 杨壮 景建发 姜颖 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种低温捕集回收废催化剂中铂族金属的方法,本发明先将铜、锑按照元素摩尔比1:(0.2～1)配制为铂族金属捕集剂,将废催化剂、造渣熔剂、捕集剂、还原剂按预定比例混匀；将混匀后的物料在1000～1200℃温度条件下熔炼,反应设定时间后渣浮于合金相表面,经渣相与合金相分离,得到含铂族金属的铜锑合金相；回收所得含铂族金属的铜锑合金相,得到铂族金属。本发明利用多金属协同捕集,铂族金属回收率高,铜、锑可形成熔化温度低于700℃的低熔点合金,降低了熔炼温度。本发明具有能耗低、成本低、回收率高等优点,有利于工业化应用。(The invention discloses a method for low-temperature trapping and recovering platinum group metals in a waste catalyst, which comprises the steps of firstly preparing copper and antimony into a platinum group metal trapping agent according to the element molar ratio of 1 (0.2-1), and uniformly mixing the waste catalyst, a slagging flux, the trapping agent and a reducing agent according to a preset proportion; smelting the uniformly mixed material at the temperature of 1000-1200 ℃, floating slag on the surface of an alloy phase after reaction for a set time, and separating the slag phase from the alloy phase to obtain a copper-antimony alloy phase containing platinum group metals; and recovering the obtained platinum group metal-containing copper-antimony alloy phase to obtain the platinum group metal. The invention utilizes the multi-metal cooperative trapping, the recovery rate of platinum group metal is high, copper and antimony can form low-melting-point alloy with the melting temperature lower than 700 ℃, and the melting temperature is reduced. The invention has the advantages of low energy consumption, low cost, high recovery rate and the like, and is beneficial to industrial application.)

1. A method for low-temperature trapping and recovering platinum group metals in waste catalysts is characterized by comprising the following steps:

(1) preparing copper and antimony into a platinum group metal trapping agent according to the element molar ratio of 1 (0.2-1), and uniformly mixing a waste catalyst, a slagging flux, the trapping agent and a reducing agent according to a preset proportion;

(2) smelting the uniformly mixed material at the temperature of 1000-1200 ℃, floating slag on the surface of an alloy phase after reaction for a set time, and separating the slag phase from the alloy phase to obtain a copper-antimony alloy phase containing platinum group metals;

(3) and recovering the obtained copper-antimony alloy phase containing the platinum group metal, and carrying out acidolysis, separation and purification treatment to obtain the platinum group metal.

2. The method for low-temperature capture and recovery of platinum group metals in waste catalysts according to claim 1, wherein in step (1), the copper is one or more of copper powder, copper oxide and copper concentrate.

3. The method for low-temperature capture and recovery of platinum group metals in waste catalyst according to claim 1, wherein in the step (1), the antimony is one or more of antimony metal powder, antimony oxide, antimony concentrate and the like.

4. The method for low-temperature trapping and recovering platinum group metals in waste catalysts according to claim 1, wherein in the step (1), the waste catalysts are waste catalysts containing platinum group metals.

5. The method for low-temperature trapping and recovering the platinum group metal in the waste catalyst according to claim 1, wherein in the step (1), the mass ratio of the waste catalyst to the trapping agent is 1 (0.1-0.4).

6. The method for low-temperature trapping and recovering the platinum group metal in the waste catalyst according to claim 1, wherein in the step (1), the reducing agent is any one or more of coke, carbon powder, graphite and coal powder.

7. The method for low-temperature capture and recovery of platinum group metals in waste catalysts according to claim 1, wherein in the step (1), the slagging flux comprises one or more of calcium oxide, magnesium oxide, calcium fluoride and borax.

8. The method for low-temperature trapping and recovering the platinum group metals in the waste catalyst according to claim 1, wherein the smelting temperature in the step (1) is 1000-1100 ℃.

Technical Field

The invention belongs to the field of platinum group metal recovery, and relates to a method for low-temperature trapping and recovering platinum group metals in a waste catalyst.

Background

The platinum group metal has excellent physical and chemical properties such as high stability, high temperature resistance, good catalytic activity and the like, and is widely applied to the fields of automobiles, petroleum, chemical engineering, aerospace and the like. But the platinum group metal reserves are small, the use amount is large, the external dependence is high, and the contradiction between supply and demand is very prominent. How to realize the high-efficiency recovery of platinum group metals from waste catalysts is a critical technology which needs to be solved urgently.

At present, methods for recovering platinum group metals from waste catalysts include wet methods and pyrogenic methods, wherein wet dissolution is mainly used, i.e., the platinum group metals are dissolved by various oxidants in an acidic environment, so that the effect of separating the platinum group metals from the carrier is achieved. However, the wet process generates a large amount of wastewater, and toxic gas is easily generated in the process of dissolving platinum group metals, so that the environmental pollution is serious.

The pyrometallurgical smelting enrichment method has the advantages of large treatment capacity, high recovery efficiency and the like, and becomes a research hotspot. Chinese invention patent (CN201510797358.6) discloses that nickel matte is used as a trapping agent, calcium oxide and silicon dioxide are used as slag formers, and platinum group metals in waste catalysts are trapped by melting at the temperature of 1400 ℃ and 1450 ℃, wherein nickel is toxic heavy metal and SO is generated in the melting process₂A gas.

The Chinese invention patent (CN103014352A) discloses a method for smelting and extracting platinum group metal from an alumina carrier petrochemical catalyst, which takes iron and copper as collectors and sodium salt as a slagging agent to collect the platinum group metal in the alumina carrier petrochemical catalyst at 1100-1450 ℃.

Chinese patent (CN112011696A) discloses a method for enriching aluminum-based waste catalyst by pyrogenic processMethod for the production of platinum group metals, using CaO-Al₂O₃-Fe₂O₃-B₂O₃The slag system is smelted, the smelting temperature is 1500-1800 ℃, the smelting temperature is high, and the energy consumption is high.

Disclosure of Invention

Aiming at the technical problems of high reagent consumption, difficult wastewater treatment, heavy metal pollution caused by a nickel-lead trapping method in pyrometallurgical smelting and high temperature and energy consumption caused by a high-temperature iron trapping method in the wet method for recovering platinum group metals from waste catalysts in the prior art, the invention aims to provide a method for low-temperature trapping and recovering platinum group metals from waste catalysts.

In order to achieve the purpose, the invention provides the following technical scheme: a method for low-temperature trapping and recovering platinum group metals in waste catalysts comprises the following steps:

(1) preparing copper and antimony into a platinum group metal trapping agent according to the element molar ratio of 1 (0.2-1), and uniformly mixing a waste catalyst, a slagging flux, the trapping agent and a reducing agent according to a preset proportion;

(2) smelting the uniformly mixed material at the temperature of 1000-1200 ℃, floating slag on the surface of an alloy phase after reaction for a set time, and separating the slag phase from the alloy phase to obtain a copper-antimony alloy phase containing platinum group metals;

(3) and recovering the obtained copper-antimony alloy phase containing the platinum group metal, and carrying out acidolysis, separation and purification treatment to obtain the platinum group metal.

Further, the copper is one or more of copper powder, copper oxide and copper concentrate; the antimony is one or more of antimony metal powder, antimony oxide and antimony concentrate.

Further, the waste catalyst is a waste catalyst containing platinum group metal.

Furthermore, the mass ratio of the waste catalyst to the trapping agent is 1 (0.1-0.4).

Further, the reducing agent is any one or more of coke, carbon powder, graphite and coal powder.

Further, the slagging flux comprises one or more of calcium oxide, magnesium oxide, calcium fluoride and borax.

Further, the smelting temperature is 1000-1100 ℃.

The invention has the advantages that:

according to a Cu-Sb phase diagram, the fact that copper and antimony can form an alloy with a low melting point can be found, the alloy with the melting temperature lower than 700 ℃ can be obtained after the composition is optimized, the copper-antimony alloy with the low melting temperature is used as a trapping agent, slag with low melting temperature and good fluidity is selected, the smelting temperature is favorably reduced, the energy consumption and the production cost are reduced, platinum group metals are more easily dissolved, the trapping capacity is stronger, the requirements on equipment and refractory materials are reduced, the industrial application is favorably realized, the recovery rate of the obtained platinum group metals is more than 99.5%, and the recovery rate of the platinum group metals is high.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

The following examples further illustrate embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples.

In the examples of the present invention, the used catalyst had the following main components: (C content 2.6 wt%, Al)₂O₃96.8 wt% Pt content 4430g/t)

Example 1

A method for low-temperature trapping and recovering platinum group metals in waste catalysts comprises the following steps:

(1) copper powder and antimony oxide are prepared into a trapping agent according to the ratio of 1: 0.2;

(2) 100 parts of platinum group metal-containing waste catalyst, 15 parts of trapping agent and 10 parts of graphite powder are mixed uniformly according to a certain proportion and then smelted in a smelting furnace, and a slagging flux is added to control the composition of molten slag (Al)₂O₃＝45％、CaO＝33％、B₂O₃22 percent), the smelting temperature is 1200 ℃, after full reaction, slag is observed to float on the surface of an alloy phase, and the copper-antimony alloy containing platinum group metal is obtained by separating the slag phase from the alloy；

(3) And recovering the obtained copper-antimony alloy phase containing the platinum group metal, carrying out acidolysis, separation and purification treatment to obtain the platinum group metal, wherein the recovery rate of the platinum group metal is more than 99.5% by detection.

Example 2

A method for low-temperature trapping and recovering platinum group metals in waste catalysts comprises the following steps:

(1) copper powder and antimony powder are prepared into a trapping agent according to the ratio of 1: 1;

(2) 100 parts of platinum group metal-containing waste catalyst, 30 parts of trapping agent and 10 parts of graphite powder are mixed uniformly according to a certain proportion and then smelted in a smelting furnace, and a slagging flux is added to control the composition of molten slag (Al)₂O₃＝38％、CaO＝43％、B₂O₃19 percent), the smelting temperature is 1000 ℃, after full reaction, slag is observed to float on the surface of an alloy phase, and the copper-antimony alloy containing platinum group metal is obtained by separating the slag phase from the alloy;

(3) and recovering the obtained copper-antimony alloy phase containing the platinum group metal, carrying out acidolysis, separation and purification treatment to obtain the platinum group metal, wherein the recovery rate of the platinum group metal is more than 99.5% by detection.

Example 3

A method for low-temperature trapping and recovering platinum group metals in waste catalysts comprises the following steps:

(1) copper powder and antimony powder are prepared into a trapping agent according to the ratio of 1: 0.5;

(2) 100 parts of platinum group metal-containing waste catalyst, 15 parts of trapping agent and 10 parts of graphite powder are mixed uniformly according to a certain proportion and then smelted in a smelting furnace, and a slagging flux is added to control the composition of molten slag (Al)₂O₃＝46％、CaO＝36％、B₂O₃18 percent) and the smelting temperature is 1100 ℃, after full reaction, slag is observed to float on the surface of an alloy phase, and the copper-antimony alloy containing platinum group metal is obtained by separating the slag phase from the alloy;

(3) and recovering the obtained copper-antimony alloy phase containing the platinum group metal, carrying out acidolysis, separation and purification treatment to obtain the platinum group metal, wherein the recovery rate of the platinum group metal is more than 99.5% by detection.

Example 4

A method for low-temperature trapping and recovering platinum group metals in waste catalysts comprises the following steps:

(1) copper powder and antimony powder are prepared into a trapping agent according to the ratio of 1: 0.8;

(2) mixing 100 parts of platinum group metal-containing waste catalyst, 10 parts of trapping agent and 10 parts of graphite powder in proportion, smelting in a smelting furnace, and adding a slagging flux to control the composition of molten slag (Al)₂O₃＝45％、CaO＝35％、B₂O₃＝10％、10CaF₂) The smelting temperature is 1100 ℃, after full reaction, slag is observed to float on the surface of an alloy phase, and the copper-antimony alloy containing platinum group metal is obtained by separating the slag phase from the alloy;

(3) and recovering the obtained copper-antimony alloy phase containing the platinum group metal, carrying out acidolysis, separation and purification treatment to obtain the platinum group metal, wherein the recovery rate of the platinum group metal is more than 99.5% by detection.

Comparative example

(1) Copper oxide is used as a trapping agent;

(2) 100 parts of platinum group metal-containing waste catalyst, 40 parts of trapping agent and 10 parts of graphite powder are mixed uniformly according to a certain proportion and then smelted in a smelting furnace, and a slagging flux is added to control the composition of molten slag (Al)₂O₃25% of CaO/SiO₂1.0), the smelting temperature is 1450 ℃, after 5 hours of reaction, slag is observed to float on the surface of an alloy phase, and the copper-based alloy containing platinum group metal is obtained by separating the slag phase from the alloy;

(3) and recovering the obtained alloy containing the platinum group metal, and performing acidolysis, separation and purification treatment to obtain the platinum group metal, wherein the recovery rate of the platinum group metal is 96.2% by detection.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.