CN1255561C - Method for preparing copper sulfate using copper concentrate - Google Patents
Method for preparing copper sulfate using copper concentrate Download PDFInfo
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- CN1255561C CN1255561C CNB2003101096592A CN200310109659A CN1255561C CN 1255561 C CN1255561 C CN 1255561C CN B2003101096592 A CNB2003101096592 A CN B2003101096592A CN 200310109659 A CN200310109659 A CN 200310109659A CN 1255561 C CN1255561 C CN 1255561C
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Abstract
The present invention discloses a method for preparing copper sulfate from copper concentrates, which comprises: compounding additives are added into copper concentrate powder, and iron in the copper concentrates and the compounding additives form double salt precipitates of basic iron sulfate during the calcining process, which are difficult to dissolve in solution of dilute sulfuric acid; when copper sulfate of calcined copper products is leached, the precipitates are filtered out together with slag, and without needing purification through iron removal, filtered solution is directly cooled for crystallization and then is filtered to obtain qualified products of copper sulfate; sulfuric acid and water are additional added into the filtered solution to regulate the density, and then, the filtered solution returns to the leaching process to achieve the purpose of recycling extracting solution. The method of the present invention overcomes the defects of complicated operation and high copper consumption of a sulfuric acid method for purification through iron removal, and the utilization ratio of copper as raw material can reach more than 96%. The method has the advantages of short technical process, simple operation, low energy consumption, recycle of all mother solution and easy industrialization.
Description
Technical Field
The invention relates to a method for preparing copper sulfate by using copper concentrate, belonging to the technical field of inorganic chemical industry.
Background
Copper sulfate is known as an important inorganic chemical raw material and has a very wide application range. In the beneficiation of nonferrous metals (copper, zinc, lead, etc.), copper sulfate is one of important agents; industrially used as mordanting agent for textiles and silk fabrics, electrolytic agent for electrolytic copper plating; is an important inorganic pesticide raw material in agriculture, can be used as an insecticide for cotton and fruit trees, a prevention and treatment agent for wheat smut and gibberellic disease, and is also a yield-increasing nutrient for a plurality of crops: can also be used as microelement additive in animal breeding feed. Because copper sulfate has wide application, the process for producing copper sulfate by using copper ore is actively researched along with the increasing price of elemental copper waste in recent years, and a plurality of new processes for producing copper sulfate by using different raw materials are successively developed. According to the search, in the existing copper sulfate production technology, CN9210259.X introduces the production of copper sulfate from waste red copper wires or copper smelting plant leftovers under the action of a copper etching auxiliary agent; the patent CN1094014A reports a method for directly preparing copper sulfate by roasting, water leaching and removing iron from calcium carbonate by using chalcopyrite; the patent CN1370742A reports a new process for preparing copper sulfate by roasting, acid leaching and extraction of copper sulfide ore; the CN1153826A patent reports a new method for producing copper sulfate by ammonia leaching of copper oxide ores. In the method for preparing the copper sulfate, the benefits are poor due to the price expansion of the waste copper wires; the iron is removed by neutralization, and the utilization rate of copper is only about 80 percent; some methods using an extracting agent have complex process; the adoption of the ammonia leaching method for leaching the copper oxide has less mineral sources and limited popularization and application. Copper ores are of various varieties and mainly divided into chalcopyrite, chalcocite, black-red copper ore and the like due to different chemical structures. The technology for developing black, red and other copper-like ores mainly containing copper oxide is that ammonia-ammonium carbonate is used as leaching agent, copper is directly leached from ores under a certain PH value condition, and pyrolyzed basic copper salt reacts with sulfuric acid to produce copper sulfate, so that the product purity and the copper utilization rate are high. Chalcopyrite, chalcocite and chalcocite are unsuitable for the above process due to their different chemical structures because these copper ores are complex in structure, insoluble in copper in dilute sulphuric acid, high in iron content and require oxidation or roasting to become soluble copper salts. The direct acid leaching by adding the oxidant not only aggravates the corrosion of equipment, but also easily pollutes the environment, has great difficulty in purifying and removing iron, and has the copper leaching rate of only 60-80 percent. Roasting-dilute sulfuric acid leaching-sponge copper method for removing iron, adding iron powder into leaching solution to reduce copper (sponge copper), roasting and oxidizing separated sponge copper, then adding sulfuric acid to prepare copper sulfate, concentrating filtrate to prepare ferrous sulfate, and the product is difficult to sell. Some documents report that ferrous iron is oxidized into ferric iron by using an oxidizing agent, then the pH value is adjusted by using an alkaline substance, and ferric iron salt is hydrolyzed and precipitated, so that the filtering treatment difficulty is large because the ferric iron salt is crystallized to be colloid, evaporation, concentration and crystallization are also needed, and a large amount of energy is consumed. Some documents use a fluidized bed furnace to roast copper ores, so that the roasting temperature is high, the operation difficulty is high, raw materials are easy to generate, and the utilization rate of copper is low. Therefore, it is a common desire of those skilled in the art to find a new method for preparing copper sulfate from copper concentrate.
Disclosure of Invention
The invention aims to provide a method for preparing copper sulfate by using copper concentrate, which simplifies the complex process of iron removal and purification of leaching solution, omits the production process of evaporation concentration, overcomes the defects of high energy consumption and raw material consumption of twice roasting and twice acid leaching, and improves the utilization rate of copper.
The method of the invention comprises the following main steps:
a. mixing the compound additive with copper concentrate powder
Putting copper concentrate powder into a mixer, adding a compound additive under stirring, and fully and uniformly mixing the copper concentrate powder with the compound additive, wherein the compound additive is Na2CO3And Na3B4O7·10H2O, the mass ratio of the two components is 2-10: 1-5;
the addition amount of the compound additive is 1-10% of the mass of the copper concentrate powder;
b. preparation of copper calcine
Placing the mixed materials into a porcelain plate, sending the porcelain plate into a radiation furnace, controlling the temperature at 550 ℃ and 600 ℃, blowing air, and roasting for 2 hours to prepare copper calcine;
c. leaching the copper calcine with sulfuric acid solution
Adding mother liquor separated from product separation section in previous cycle into leaching kettle, and using residueAdjusting pH of the leaching solution to not less than 2 with washing solution, industrial sulfuric acid and water, and maintaining the density at 1200kg · m-3Heating to 80 deg.C, adding copper calcine into leaching kettle at solid-liquid mass ratio of 1: 2.5-3.5, heating to 85-90 deg.C, stirring at constant temperature for 1.5 hr, blowing air into the system, leaching for 0.5 hr for 2 hr to maintain the density of leaching solution at not more than 1400 kg.m-3Obtaining leaching solution containing copper sulfate;
d. solid-liquid separation and cooling crystallization
Heating the temperature of the leaching solution to 95 ℃, filtering while the solution is hot, sending the filtrate into a crystallization kettle, cooling to 25 ℃, cooling for crystallization, and centrifuging and drying to obtain a copper sulfate product;
e. the mother liquor returns to the leaching working section for recycling
The mother liquor filtered out from the copper sulfate product is returned to the leaching working section and is recycled as leaching solution.
In the preparation method of the invention, the compound additive Na2CO3And Na3B4O7·10H2The proper mixing proportion of O is 2-5: 1-2 according to the mass ratio.
The more proper addition amount of the compound additive is 2-5% of the mass of the copper concentrate powder.
According to the method, the compound additive is heated and dissolved by water, and then added into the copper concentrate powder to be mixed for 15 minutes.
The method of the invention has the copper calcine leaching temperature of 85-90 ℃ and the leaching time of 1.5-2 hours.
The key point of the technology of the invention is that after the complex additive is added into the copper concentrate powder, the iron can form basic trivalent iron complex salt in the roasting process, the iron salt is not dissolved in dilute sulphuric acid, and is filtered out along with the residue in the leaching process, and the main reaction is as follows:
under strong oxidative conditions:
because iron is more reactive than copper, the following reaction occurs quickly:
under the catalytic action of high temperature and borax, ferric sulfate reacts as follows:
the alkaline complex ferrite precipitate is insoluble in dilute sulfuric acid during leaching and is filtered out together with the residue. The leaching solution has little iron content, can be completely and directly cooled and crystallized, and omits a complex process of purifying and removing iron. Under the reducing condition, ferric sulfate reacts with chalcopyrite to generate ferrous iron, and a small amount of ferrous sulfate is still contained in leaching solution, so that under the condition of regulating the pH value to be more than 2 in the leaching process, air is blown to oxidize the ferric sulfate to change the ferric sulfate into ferric sulfate, the ferric sulfate is hydrolyzed and precipitated, and the ferric sulfate is filtered out along with residues when the ferric sulfate is hot.
The technical progress achieved by the invention is as follows: the invention overcomes the defects of complex operation and high copper consumption of iron removal and purification by a sulfuric acid method, has the utilization rate of raw material copper up to over 96 percent (by mass), short process flow, simple operation, low energy consumption, complete cyclic utilization of mother liquor and easy industrial implementation.
Drawings
FIG. 1 shows a process flow diagram of the present invention.
Detailed Description
The following examples illustrate the invention.
Example 1
The method comprises the steps of taking brass concentrate powder in Shanxi China as a raw material, putting 500g of copper ore concentrate powder into a mixer, starting stirring, slowly dripping 15g of prepared compound additive (dissolved in 50g of water) into the copper ore powder, stirring for a certain time, putting into a ceramic disc, putting into a radiation furnace, roasting at 600 ℃ for 2 hours under the condition of blast air, cooling and discharging to obtain copper calcine, wherein the copper ore powder has the copper content of 23.12% (mass fraction) and the fineness of 60 meshes and 95%. Adding 1000g of water into a leaching kettle with the effective volume of 2000ml, adding 93 percent (mass fraction) of sulfuric acid 20g, stirring and heating to 80 ℃, adding copper calcine, heating to 90 ℃, timing, stirring and leaching at constant temperature for 1.5h, starting to blow air to the system, leaching for 2h, filtering while hot, sending filtrate to a crystallization kettle, directly cooling to 25 ℃ for crystallization, and centrifugally spin-drying to obtain a product, namely 310g of copper sulfate pentahydrate, with the content of 96.18 percent (mass fraction), 950g of mother liquor and 14 percent (mass fraction) of copper sulfate pentahydrate; 100g (mass fraction) of the residue cleaning solution contained 0.6% of copper, and the total copper yield was 96.13% (by mass).
Example 2
Using concentrated bright copper ore powder of Hebei China as raw material, copper content is 17.68% (mass fraction), copper ore powder with fineness of 60 meshes and 90%, putting 500g of the concentrated copper ore powder into a mixer, starting stirring, slowly dripping 10g of prepared compound additive (dissolved in 50g of water) into the ore powder, stirring for a certain time, putting into a porcelain plate, putting into a radiant furnace, roasting at 550 ℃ for 2h under the condition of blast air, cooling and discharging to obtain copper calcine for later use. Adding the mother liquor obtained in the example 1 into a leaching kettle with an effective volume of 2000ml, adjusting the pH value and the density of the leaching solution by using residue washing liquor and sulfuric acid, stirring and heating to 80 ℃, adding copper calcine, heating to 90 ℃, timing, stirring and leaching at constant temperature for 1.5h, starting to blow air to a system, leaching for 2h, filtering while hot, sending filtrate into a crystallization kettle for direct cooling and crystallization, and centrifugally spin-drying to obtain a product copper sulfate 346g with the content of 96.38 percent (mass fraction), mother liquor 960g and copper sulfate pentahydrate 13.8 percent (mass fraction); 100g of residue washing liquid, 0.61% of copper (mass fraction), and 97.7% of total reduced copper yield (by mass).
Claims (4)
1. A method for preparing copper sulfate by using copper concentrate is characterized by comprising the following steps:
a. mixing the compound additive with copper concentrate powder
Putting copper concentrate powder into a mixer, adding a compound additive under stirring to be fully mixed with the copper concentrate powder, wherein the compound additive is Na2CO3And Na2B4O7·10H2O, the mass ratio of the two components is 2-10: 1-5;
the addition amount of the compound additive is 1-10% of the mass of the copper concentrate powder;
b. preparation of copper calcine
Placing the mixed copper concentrate powder into a porcelain plate, sending the porcelain plate into a radiation furnace, controlling the temperature at 550 ℃ and 600 ℃, blowing air, and roasting for 2 hours to prepare copper calcine;
c. leaching the copper calcine with sulfuric acid solution
Adding 1000gof water and 93% sulfuric acid 20g into leaching kettle, adjusting pH of the leaching solution to not less than 2, and maintaining the density at 1200kg · m-3Heating to 80 deg.C, adding copper calcine into leaching kettle at solid-liquid mass ratio of 1: 2.5-3.5, heating to 85-90 deg.C, stirring at constant temperature for 1.5 hr, blowing air into the system, and leaching for 0.5 hr to maintain the density of leaching solution at not more than 1400 kg.m-3Obtaining leaching solution containing copper sulfate;
d. solid-liquid separation and cooling crystallization
Heating the temperature of the leaching solution to 95 ℃, filtering while the solution is hot, sending the filtrate into a crystallization kettle, cooling to 25 ℃, cooling for crystallization, and centrifuging and drying to obtain a copper sulfate product;
e. the mother liquor returns to the leaching working section for recycling
The mother liquor filtered out from the copper sulfate product is returned to the leaching working section and is recycled as leaching solution.
2. The method according to claim 1, wherein the compound additive Na2CO3And Na2B4O7·10H2The mass ratio of the O is 2-5: 1-2.
3. The method according to claim 1, characterized in that the additive amount of the compound additive is 2-5% of the mass of the copper concentrate powder.
4. A process according to claim 1, 2 or 3, characterized in that the built-up additive is dissolved in water under heating, added to the copper concentrate powder and mixed for 15 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101096592A CN1255561C (en) | 2003-11-13 | 2003-11-13 | Method for preparing copper sulfate using copper concentrate |
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| CNB2003101096592A CN1255561C (en) | 2003-11-13 | 2003-11-13 | Method for preparing copper sulfate using copper concentrate |
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| CN1544663A CN1544663A (en) | 2004-11-10 |
| CN1255561C true CN1255561C (en) | 2006-05-10 |
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| CNB2003101096592A Expired - Fee Related CN1255561C (en) | 2003-11-13 | 2003-11-13 | Method for preparing copper sulfate using copper concentrate |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328542B (en) * | 2008-07-25 | 2010-06-02 | 紫金矿业集团股份有限公司 | Method for directly preparing copper sulfate and cathode copper from copper ore concentrate |
| CN103074499B (en) * | 2013-01-31 | 2014-07-30 | 云南驰宏锌锗股份有限公司 | Method for producing high-quality copper sulfate through low-pressure oxygen leaching of copper slag |
| CN103773946B (en) * | 2014-01-13 | 2016-04-13 | 江西理工大学 | Chalcopyrite alkali fusion refining pre-treatment-low temperature pressure leaching process |
| CN113401932A (en) * | 2021-05-26 | 2021-09-17 | 中化地质矿山总局地质研究院 | Preparation method of copper sulfate pentahydrate |
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