阅读说明：本技术 一种铼浸出渣中铜铋分离回收方法 (Method for separating and recovering copper and bismuth in rhenium leaching residues ) 是由 牛永胜 邵丽 李银丽 姚夏妍 李玉 王源瑞 刘静静 于 2019-08-19 设计创作，主要内容包括：本发明属于化工技术领域,涉及一种铼浸出渣中铜铋分离回收方法。其包括碱法脱砷、超声氧化酸浸脱铜、超声氯盐酸浸铋以及水解沉铋。本发明先采用碱浸脱除铼浸出渣中的砷,且砷脱除率达到了99.9%,基本消除了砷对制备出的氯氧化铋产品纯度的影响；在铼浸出渣脱铜及浸铋工序中采用了超声装置,实现了铜铋的高效分离,铜、铋的回收率分别达到了98.5%和93.4%。(The invention belongs to the technical field of chemical industry, and relates to a method for separating and recovering copper and bismuth in rhenium leaching residues. The method comprises the steps of arsenic removal by an alkaline method, copper removal by ultrasonic oxidation and acid leaching, bismuth leaching by ultrasonic chlorine hydrochloric acid and bismuth precipitation by hydrolysis. According to the method, the arsenic in the rhenium leaching residue is removed by alkaline leaching, the removal rate of the arsenic reaches 99.9%, and the influence of the arsenic on the purity of the prepared bismuth oxychloride product is basically eliminated; an ultrasonic device is adopted in the working procedures of copper removal of rhenium leaching residues and bismuth leaching, so that the high-efficiency separation of copper and bismuth is realized, and the recovery rates of copper and bismuth reach 98.5 percent and 93.4 percent respectively.)

1. A method for separating and recovering copper and bismuth in rhenium leaching residues is characterized by comprising the following steps:

a. removing arsenic by an alkaline method: adding rhenium leached residues into a reaction kettle, then adding caustic soda solution with the concentration of 0.11g/ml, wherein the mass ratio of the rhenium leached residues to sodium hydroxide is 1:0.44, heating by steam, keeping the temperature at 70-90 ℃, reacting for 30min, and filtering to obtain dearsenifying liquid and dearsenifying residues, wherein the rhenium leached residues and the rhenium leached residues are mixed;

b. oxidation acid leaching decoppering: putting the arsenic-removed slag into an ultrasonic reaction kettle, and then adding sulfuric acid with the concentration of 98% and hydrogen peroxide with the concentration of 30%, wherein the mass-to-volume ratio of the arsenic-removed slag to the sulfuric acid is 6:5, and the mass-to-volume ratio of the arsenic-removed slag to the hydrogen peroxide is 6: 7; heating the ultrasonic reaction kettle, keeping the temperature at 60-95 ℃, starting an ultrasonic generating device, reacting for 20min under the conditions of ultrasonic power of 50-150W and ultrasonic frequency of 5-80kHz, and filtering to obtain a copper sulfate solution and decoppered slag;

c. acid leaching of bismuth by chloride hydrochloric acid: putting the decoppered slag into an ultrasonic reaction kettle, and adding hydrochloric acid with the concentration of 36% and sodium chloride, wherein the mass-to-volume ratio of the decoppered slag to the hydrochloric acid is 1:1, and the mass ratio of the decoppered slag to the sodium chloride is 5: 1; heating an ultrasonic reaction kettle, keeping the temperature at 60-75 ℃, starting an ultrasonic generating device, reacting for 10min under the conditions of ultrasonic power of 20-200W and ultrasonic frequency of 10-50kHz, and filtering to obtain bismuth leaching solution and bismuth leaching slag;

d. hydrolyzing and precipitating bismuth: and adding barium salt to the hydrolysis immersion bismuth liquid to remove sulfate radical, adding a sodium hydroxide dilute solution to adjust the pH of the solution to be =3, carrying out hydrolysis reaction on the bismuth trichloride solution to generate bismuth oxychloride white precipitate, and washing and drying to obtain the bismuth oxychloride solid.

Technical Field

The invention belongs to the technical field of chemical industry, and relates to a method for separating and recovering copper and bismuth in rhenium leaching residues.

Background

Copper smelting sulfuric acid systems produce large quantities of contaminated acid each year, containing relatively high concentrations of valuable metallic rhenium, and produce large quantities of rhenium leaching residues containing relatively high amounts of copper (6-10%) bismuth (40%) during precipitation and oxidative leaching for the recovery of valuable metallic rhenium. At present, copper smelting enterprises generally only recover copper in the bismuth-containing slag by returning the bismuth-containing slag to a smelting system, so that impurities such As As, Bi and the like form vicious circle in the smelting system and are continuously enriched, the aim of comprehensive utilization cannot be achieved, and the electrolytic process contains bismuth with higher concentration, so that the electro-crystallization growth form of deposited copper and the unit cell parameters of a copper deposition layer are changed, the phenomenon of long particles of cathode copper is caused, and the quality of the cathode copper is seriously influenced.

Disclosure of Invention

The invention aims to provide a method for efficiently separating and recovering copper and bismuth in rhenium leaching residues aiming at the problems in the prior art.

The specific technical scheme of the invention is as follows:

a method for separating and recovering copper and bismuth in rhenium leaching residues is characterized by comprising the following steps:

a. removing arsenic by an alkaline method: adding rhenium leached residues into a reaction kettle, then adding caustic soda solution with the concentration of 0.11g/ml, wherein the mass ratio of the rhenium leached residues to sodium hydroxide is 1:0.44, heating by steam, keeping the temperature at 70-90 ℃, reacting for 30min, and filtering to obtain dearsenifying liquid and dearsenifying residues, wherein the rhenium leached residues and the rhenium leached residues are mixed;

b. oxidation acid leaching decoppering: putting the arsenic-removed slag into an ultrasonic reaction kettle, and then adding sulfuric acid with the concentration of 98% and hydrogen peroxide with the concentration of 30%, wherein the mass-to-volume ratio of the arsenic-removed slag to the sulfuric acid is 6:5, and the mass-to-volume ratio of the arsenic-removed slag to the hydrogen peroxide is 6: 7; heating the ultrasonic reaction kettle, keeping the temperature at 60-95 ℃, starting an ultrasonic generating device, reacting for 20min under the conditions of ultrasonic power of 50-150W and ultrasonic frequency of 5-80kHz, and filtering to obtain a copper sulfate solution and decoppered slag;

c. acid leaching of bismuth by chloride hydrochloric acid: putting the decoppered slag into an ultrasonic reaction kettle, and adding hydrochloric acid with the concentration of 36% and sodium chloride, wherein the mass-to-volume ratio of the decoppered slag to the hydrochloric acid is 1:1, and the mass ratio of the decoppered slag to the sodium chloride is 5: 1; heating an ultrasonic reaction kettle, keeping the temperature at 60-75 ℃, starting an ultrasonic generating device, reacting for 10min under the conditions of ultrasonic power of 20-200W and ultrasonic frequency of 10-50kHz, and filtering to obtain bismuth leaching solution and bismuth leaching slag;

d. hydrolyzing and precipitating bismuth: and adding barium salt to the hydrolysis immersion bismuth liquid to remove sulfate radical, adding a sodium hydroxide dilute solution to adjust the pH of the solution to be =3, carrying out hydrolysis reaction on the bismuth trichloride solution to generate bismuth oxychloride white precipitate, and washing and drying to obtain the bismuth oxychloride solid.

The principle of the invention is as follows: the leaching process of the arsenic-removing slag and the copper leaching slag accelerates the reaction process through ultrasonic treatment. Mainly due to the cavitation effect of the ultrasonic waves, cavitation nuclei are formed when high-intensity ultrasonic waves pass through liquid. When the cavitation nuclei accumulate high enough energy to collapse and close, extremely brief intense pressure pulses are generated around the cavitation nuclei at the moment of collapse, creating an abnormally high temperature (5000K) and high pressure (50 MPa) local environment inside the liquid. Particularly, due to the ultrasonic cavitation effect close to the solid-liquid interface, the micro jet generated when bubbles collapse can cause ultrasonic damage (pitting) on the surface of the solid, and can also enable micro solid particles to collide at high speed, so that the chemical reaction is accelerated.

The invention has the following beneficial effects: according to the method, the arsenic in the rhenium leaching residue is removed by alkaline leaching, the removal rate of the arsenic reaches 99.9%, and the influence of the arsenic on the purity of the prepared bismuth oxychloride product is basically eliminated; an ultrasonic device is adopted in the working procedures of copper removal of rhenium leaching residues and bismuth leaching, so that the high-efficiency separation of copper and bismuth is realized, and the recovery rates of copper and bismuth reach 98.5 percent and 93.4 percent respectively.

Drawings

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

Detailed Description

And (3) carrying out copper-bismuth separation on rhenium leaching residues, wherein the components of the rhenium leaching residues are shown in a table 1:

。