阅读说明：本技术 一种从含铜废石中生产高品级硫酸铜的方法 (Method for producing high-grade copper sulfate from copper-containing waste stone ) 是由 王永智 张析 寇明遥 王瑞芳 王进龙 齐艳妮 王军 牟业龙 于 2021-08-18 设计创作，主要内容包括：本发明公开了一种从含铜废石中生产高品级硫酸铜的方法,该方法包括如下步骤：以含铜废石为原料,在酸性条件下使用选育出来的高效浸矿菌BY3#细菌种群组合进行生物浸出,过滤得浸出液；浸出液采用铜萃取剂进行萃取、硫酸溶液反萃；反萃液蒸发浓缩、离心过滤干燥得到高品级硫酸铜。本发明的方法工艺简单,技术先进,回收制备的硫酸铜纯度高,可对铜废石资源合理开发利用。(The invention discloses a method for producing high-grade copper sulfate from copper-containing waste rock, which comprises the following steps: taking copper-containing waste rock as a raw material, performing biological leaching BY using the bred high-efficiency leaching bacteria BY3# bacterial population combination under an acidic condition, and filtering to obtain a leaching solution; extracting the leachate by using a copper extractant and back extracting the leachate by using a sulfuric acid solution; the back extraction solution is evaporated, concentrated, centrifugally filtered and dried to obtain high-grade copper sulfate. The method has simple process and advanced technology, the purity of the recovered and prepared copper sulfate is high, and the method can reasonably develop and utilize copper waste rock resources.)

1. A method for producing high-grade copper sulfate from copper-containing waste rock is characterized by comprising the following steps:

1) bioleaching, namely leaching the copper-containing waste rock BY using a sulfuric acid solution and a combined leaching solution of a bacterial population of the high-efficiency mineral leaching bacteria BY3# and performing vacuum filtration to obtain a leaching filtrate and filter residue;

2) extracting copper, namely adding a copper extractant LIX841 into the leaching filtrate to perform reactive extraction on the copper, so as to obtain an extracted copper loaded organic phase and raffinate;

3) back extraction, namely adding a sulfuric acid solution into the copper-containing loaded organic phase for back extraction to obtain a back extraction solution and a back extraction organic phase;

4) preparing copper sulfate, namely performing vacuum concentration on the back extraction solution obtained in the step 3), crystallizing the concentrated solution, filtering, washing and drying to obtain copper sulfate crystals;

5) and washing and drying the copper sulfate crystals to obtain high-grade copper sulfate.

2. The method for producing high-grade copper sulfate from copper-containing waste rock as claimed in claim 1, wherein the ore grinding fineness of the copper-containing waste rock in the bioleaching in the step 1) is-120 mesh 80%; the waste stone leaching solution is a sulfuric acid solution with the pH value of 1.5 and a combined leaching solution of a bacterial population of the high-efficiency mineral leaching bacteria BY3, the leaching temperature is 40-60 ℃, and the leaching time is 30-45 days.

3. The method for producing high-grade copper sulfate from copper-containing waste rock as claimed in claim 1, wherein the extractant in step 2) is LIX841 or LIX 984.

4. The method as claimed in claim 1, wherein the concentration of sulfuric acid solution in step 3) is 150-180 g/l.

5. The method for producing high-grade copper sulfate from copper-containing waste rock as claimed in claim 1, wherein the specific gravity of the solution after concentration in the step 4) reaches 1.40g/ml, water cooling crystallization is carried out, and the crystallized solution is filtered to obtain copper sulfate crystals and filtrate.

6. The method of claim 1, wherein the copper sulfate is produced from copper-bearing waste rock by: in the step 1), the grade of the selected copper-containing waste rock is not less than 0.2%.

7. The method of claim 1, wherein the copper sulfate is produced from copper-bearing waste rock by: in the step 1), the bacterial population of the high-efficiency mineral leaching bacteria BY3 is mesophilic bacteria.

8. The method of claim 1, wherein the copper sulfate is produced from copper-bearing waste rock by: in the step 1), the leaching time is 30-45 days, 1/3 leachate is pumped out every 10-15 days for collection, and 1/3 fresh combined leachate is added.

Technical Field

The invention relates to the technical field of ore resource recycling, in particular to a method for producing high-grade copper sulfate from copper-containing waste rock.

Background

About 2 hundred million tons of copper waste rock, about 0.2 percent of copper grade and about 40 ten thousand tons of copper-containing metal are recovered in a mine, and if the part of copper resources are recovered, the copper resources are equivalent to the copper storage capacity of a new small copper ore deposit. The large amount of stockpiled ores release a large amount of heavy metal ions under the natural oxidation action, seriously pollute local soil and water resources and have great threat to the local environmental safety. Therefore, the once abandoned resources are utilized, and not only the waste is changed into valuable, so that the comprehensive utilization level of the resources is improved, and the resource reserves are increased; meanwhile, the environment-friendly quality of the mine is improved, the hidden danger of environmental pollution is reduced and even eliminated, and the social benefit is remarkable.

The bioleaching technology is a preferred process for processing low-grade ores by various mine metallurgy investment enterprises due to the advantages of simple process, capability of directly extracting high-purity metal from low-grade ores and the like and the obvious advantages in the aspects of economic benefit and environmental protection. Up to now, the yield of electrodeposited copper produced by the world countries using the bio-immersion copper technology has exceeded millions of tons and has grown at a rate of 5.4% per year.

Copper sulfate is one of the most important copper salts of copper compounds, and it has a wide range of uses. In agriculture, copper sulfate is an important inorganic pesticide raw material, such as prepared Bordeaux mixture, which is an insecticide for cotton and fruit trees, and can also be used for producing other copper-containing pesticides for preventing and treating smut, gibberellic disease and the like of wheat, and the copper sulfate is used for preparing copper-containing micro-fertilizer which has yield-increasing effect on many crops. Copper sulfate is also an important trace element additive for animal feed. In the chemical industry, copper sulfate is used as mordant, wood preservative, coating and the like for cotton and silk fabrics. In the beneficiation of nonferrous metals, copper sulfate is one of important medicaments. With the rapid development of non-metal plating, decorative plating and printed circuit boards in China, the demand of plating-grade copper sulfate is rapidly increased. Therefore, the waste copper resources are recycled to prepare high-quality copper sulfate, so that the copper ore resources are fully utilized, and the method has better economic benefit.

Disclosure of Invention

The invention aims to provide a method for producing high-grade copper sulfate from copper-containing waste rock, which has advanced process, high purity of the recovered and prepared copper sulfate and reasonable development and utilization of copper waste rock resources.

The invention solves the technical problems by the following technical means:

a method for producing high-grade copper sulfate from copper-containing waste rock comprises the following steps:

bioleaching, namely leaching the copper-containing waste rock BY using a sulfuric acid solution and a combined leaching solution of a bacterial population of the high-efficiency mineral leaching bacteria BY3# and performing vacuum filtration to obtain a leaching filtrate and filter residue;

extracting copper, namely adding a copper extractant LIX841 into the leaching filtrate to extract copper to obtain an extracted copper loaded organic phase and raffinate;

back extraction, namely adding a sulfuric acid solution (150-180 g/l) into the copper-containing loaded organic phase for back extraction to obtain a back extraction solution and a back extraction organic phase;

and (3) preparing copper sulfate, concentrating the back extraction solution in vacuum, crystallizing the concentrated solution, filtering, washing and drying to obtain a copper sulfate solid.

Further, the bioleaching equipment is a PVC leaching column with the diameter of 0.5 meter and the height of 5 meters, and the ground copper-containing waste rock is filled into 3/4 parts in the column.

Further, in the bioleaching step, the grinding fineness of the copper-containing waste stone is 80 percent of minus 120 meshes, the leaching solution is a sulfuric acid solution with the pH of 1.5 and the bacterial population of the high-efficiency mineral leaching bacteria BY3# for combined leaching, the leaching solution surface is 10cm higher than the filled waste stone, the leaching temperature is 40-60 ℃, and the leaching time is 30-45 days;

further, in the process of leaching for 30-45 days, 1/3 leachate is pumped out and collected every 10-15 days, and 1/3 fresh combined leachate is added.

Further, the leachate collected in the bioleaching process is subjected to vacuum filtration to obtain leaching filtrate and filter residue.

Further, adding a copper extractant into the filtrate obtained by bioleaching, wherein the extractant is LIX841 or LIX984, so as to obtain an extracted copper loaded organic phase and raffinate;

further, the copper-loaded organic phase separated after extraction is added with 150-180g/l sulfuric acid solution for back extraction to obtain a back extraction solution and a back extraction organic phase.

Further, vacuum concentrating the separated back extraction solution with a rotary evaporator at-60 MP and 60-65 deg.C, wherein the specific weight of the solution before evaporation is 1.14-1.18 g/m³The early stage of the specific gravity of the evaporated liquid is controlled to be 1.40-1.50 g/m³。

Further, cooling and crystallizing the evaporated solution, and filtering the crystallized solution when the temperature of the crystallized solution is 30 ℃ to obtain copper sulfate crystals.

And further, washing the copper sulfate crystal obtained after filtering with deionized water, performing suction filtration, and drying in a drying oven to obtain high-grade copper sulfate.

The invention has the beneficial effects that:

according to the invention, the copper-containing waste rock is leached BY combining the acid solution and the high-efficiency leaching bacteria BY3# bacterial population, so that copper ions in the copper-containing waste rock are completely dissolved into the leaching solution as much as possible, and the leaching rate is high.

According to the invention, copper ions in the leachate are extracted by using a copper extractant LIX841, and then desorbed by using a sulfuric acid solution to obtain a desorption solution with higher copper ion content and lower other impurities; further improving the purity of the copper sulfate.

The method has simple process and advanced technology, the purity of the recovered and prepared copper sulfate is high, and the method can reasonably develop and utilize copper waste rock resources.

Drawings

FIG. 1 is a schematic flow diagram of a process for producing high grade copper sulfate from copper-containing waste rock according to the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable.

Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.

Example 1

The invention relates to a method for producing high-grade copper sulfate from copper-containing waste rock, which comprises the following specific steps:

the grinding fineness of the copper waste stone is 80 percent of-120 meshes.

Biologically leaching, namely leaching copper-containing waste stone (grade 0.21%) BY using a sulfuric acid solution with the pH of 1.5 and a combined leaching solution of a bacterial population of efficient mineral leaching bacteria BY3, wherein the leaching temperature is 45 ℃, the leaching time is 40 days, and vacuum filtering is performed to obtain leaching filtrate and filter residue;

thirdly, copper is extracted, a copper extractant LIX841 is added into the leaching filtrate obtained in the second step to extract copper, and an extracted copper-bearing loaded organic phase and raffinate are obtained;

step four, adding a sulfuric acid solution (with the concentration of 150 g/l) into the copper-containing loaded organic phase obtained in the step three for back extraction to obtain a back extraction solution (with the specific gravity of 1.14 g/m)³) And stripping the organic phase;

preparing copper sulfate, and carrying out vacuum evaporation and concentration on the back extraction solution obtained from the fourth step until the specific gravity of the solution is 1.45 g/m³And uniformly stirring, cooling and crystallizing (the end point temperature is 30 ℃), filtering, washing and drying to obtain a copper sulfate solid.

Sixthly, returning the filtered solution to the step three, and extracting copper.

The purity of the copper sulfate crystal obtained by the method reaches 98.4 percent, and the impurity components are shown in table 1:

TABLE 1 copper sulfate component content

Example 2

The invention relates to a method for producing high-grade copper sulfate from copper-containing waste rock, which comprises the following specific steps:

the grinding fineness of the copper waste stone is 80 percent of-120 meshes.

Biologically leaching, namely leaching copper-containing waste stone (grade 0.23%) BY using a sulfuric acid solution with the pH of 1.5 and a combined leaching solution of a bacterial population of efficient mineral leaching bacteria BY3, wherein the leaching temperature is 50 ℃, the leaching time is 35 days, and vacuum filtering is performed to obtain leaching filtrate and filter residue;

extracting copper, namely adding a copper extractant LIX984 into the leaching filtrate obtained in the step II to extract copper to obtain an extracted copper-containing loaded organic phase and raffinate;

step four, back extraction, namely adding a sulfuric acid solution (with the concentration of 150 g/l) into the copper-containing loaded organic phase obtained in the step three for back extraction to obtain a back extraction solution (with the specific gravity of 1.16 g/m)³) And stripping the organic phase;

preparing copper sulfate, and carrying out vacuum evaporation and concentration on the back extraction solution obtained from the fourth step until the specific gravity of the solution is 1.45 g/m³And uniformly stirring, cooling and crystallizing (the end point temperature is 30 ℃), filtering, washing and drying to obtain a copper sulfate solid.

Sixthly, returning the filtered solution to the step three, and extracting copper.

The purity of the copper sulfate crystal obtained by the method reaches 98.7 percent, and the impurity components are shown in table 2:

TABLE 2 copper sulfate component content

Example 3

The invention relates to a method for producing high-grade copper sulfate from copper-containing waste rock, which comprises the following specific steps:

the grinding fineness of the copper waste stone is 80 percent of-120 meshes.

Biologically leaching, namely leaching copper-containing waste stone (grade 0.195%) BY using a sulfuric acid solution with the pH of 1.5 and a combined leaching solution of a bacterial population of efficient mineral leaching bacteria BY3, wherein the leaching temperature is 55 ℃, the leaching time is 45 days, and vacuum filtering is performed to obtain leaching filtrate and filter residue;

thirdly, copper is extracted, a copper extractant LIX841 is added into the leaching filtrate obtained in the second step to extract copper, and an extracted copper-bearing loaded organic phase and raffinate are obtained;

step four, back extraction, namely adding a sulfuric acid solution (with the concentration of 150 g/l) into the copper-containing loaded organic phase obtained in the step three for back extraction to obtain a back extraction solution (with the specific gravity of 1.12 g/m)³) And stripping the organic phase;

preparing copper sulfate, and carrying out vacuum evaporation and concentration on the back extraction solution obtained from the fourth step until the specific gravity of the solution is 1.45 g/m³And uniformly stirring, cooling and crystallizing (the end point temperature is 30 ℃), filtering, washing and drying to obtain a copper sulfate solid.

Sixthly, returning the filtered solution to the step three, and extracting copper.

The purity of the copper sulfate crystal obtained by the method reaches 98.5 percent, and the impurity components are shown in Table 3:

TABLE 3 copper sulfate component content

The invention has the following advantages:

the method can realize the recycling of the solution and avoid the discharge of wastewater.

The method has the advantages that the purity of the prepared copper sulfate crystal is high, and the economic benefit is good.

The method has simple process and advanced technology, and can reasonably develop and utilize the copper waste rock resources.

Although the present invention has been described in detail with reference to the preferred embodiments, it should be noted that modifications to the specific embodiments of the present invention may be made by those skilled in the art without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.