阅读说明：本技术 金银选矿剂、金银选矿剂的制备方法及其应用 (Gold and silver beneficiation agent, preparation method and application thereof ) 是由 陆云骏 于 2020-11-04 设计创作，主要内容包括：本发明公开一种金银选矿剂、金银选矿剂的制备方法及其应用,涉及矿物浮选技术领域。所述金银选矿剂包括以下组分：亚铁氰化钠、尿素、硫脲、氢氧化钠、碳酸钠、硫化钠以及亚硫酸钠。本发明提出的金银选矿剂,在选矿时,金银选矿剂中的活性组分与矿石中的金或银形成络合物,使得金或银从矿石中进入到溶液中,实现了金或银的浸出,具有无毒、便于生产,成本低廉的优点,用于金银选矿时,降低了成本且毒性更小。(The invention discloses a gold and silver beneficiation agent, a preparation method and application thereof, and relates to the technical field of mineral flotation. The gold and silver beneficiation agent comprises the following components: sodium ferrocyanide, urea, thiourea, sodium hydroxide, sodium carbonate, sodium sulfide and sodium sulfite. According to the gold and silver beneficiation agent provided by the invention, during beneficiation, active components in the gold and silver beneficiation agent and gold or silver in ores form a complex, so that the gold or silver enters a solution from the ores, the gold or silver leaching is realized, and the gold and silver beneficiation agent has the advantages of no toxicity, convenience in production and low cost, and is used for gold and silver beneficiation, so that the cost is reduced and the toxicity is lower.)

1. The gold and silver beneficiation agent is characterized by comprising the following components:

sodium ferrocyanide, urea, thiourea, sodium hydroxide, sodium carbonate, sodium sulfide and sodium sulfite.

2. The gold and silver beneficiation agent according to claim 1, wherein the gold and silver beneficiation agent comprises the following components in parts by weight:

5-10 parts of sodium ferrocyanide, 15-40 parts of urea, 8-18 parts of thiourea, 6-10 parts of sodium hydroxide, 10-20 parts of sodium carbonate, 2-5 parts of sodium sulfide and 2-5 parts of sodium sulfite.

3. A process for the preparation of a beneficiation agent for gold and silver according to any one of claims 1 to 2, characterized by comprising the following steps:

s10, adding urea and thiourea into a closed container, heating for the first time to completely melt the materials, then continuously adding sodium hydroxide, sodium carbonate, sodium ferrocyanide, sodium sulfide and sodium sulfite into the closed container, continuously heating for the second time to completely melt the materials, and then keeping the temperature to obtain a melt;

and S20, cooling and crushing the melt to obtain the gold and silver beneficiation agent.

4. The method for preparing a gold and silver beneficiation agent according to claim 3, wherein in step S10, the heating temperature of the first heating is 180 ℃ to 200 ℃.

5. The method for preparing a gold and silver beneficiation agent according to claim 3, wherein in step S10, the heating temperature of the second heating is 800 ℃ to 900 ℃.

6. The method for preparing the gold and silver beneficiation agent according to claim 3, wherein in step S10, the conditions of the heat preservation are as follows: keeping the temperature at 800-900 ℃ for 2-3 h.

7. The method of preparing a gold and silver beneficiation agent according to claim 3, further comprising:

and S30, treating the tail gas generated in the closed container.

8. The preparation method of the gold and silver beneficiation agent according to claim 7, wherein the step S30 specifically comprises:

and cooling the tail gas, and introducing the tail gas into a sodium chloride solution for reaction to obtain a mixed solution.

9. A beneficiation method is characterized by comprising the following steps:

grinding ores containing gold and/or silver, and sequentially adding a gold and silver beneficiation agent and water to form ore pulp;

adjusting the pH value of the ore pulp to 10-11.5, continuously stirring the ore pulp for 24 hours, and carrying out solid-liquid separation to obtain a leaching solution, wherein the leaching solution contains a leaching crude product of gold and/or silver;

the gold and silver beneficiation agent is the gold and silver beneficiation agent according to any one of claims 1 to 2.

10. A beneficiation method according to claim 9, wherein in the step of grinding the ore containing gold and/or silver, and adding a gold and silver beneficiation agent and water in this order to form a pulp, the mass ratio of the gold and silver beneficiation agent to the ore containing gold and/or silver is (1.5 to 3.9) kg: 1 t.

Technical Field

The invention relates to the technical field of mineral flotation, in particular to a gold and silver beneficiation agent, a preparation method of the gold and silver beneficiation agent and application of the gold and silver beneficiation agent.

Background

Since the 19 th century, cyanide is widely used for leaching gold and silver ores, and the method has the advantages of simple process operation, low medicament consumption and low production cost. However, cyanide also has many disadvantages in leaching gold and silver ores, such as: the leaching rate of the gold mineral coated by the fine particles is low; the high-grade tailings leached by cyanidation are difficult to sort; the requirements of cyanide as a hazardous chemical in the use and transportation process are strict; the use of cyanide is serious in environmental pollution.

In order to solve various defects of cyanide, a large amount of research work on environment-friendly medicaments is carried out at home and abroad to find novel environment-friendly medicaments which are more effective, convenient, low-toxicity and can replace cyanide. To date, several tens of environmentally friendly leaching agents have been studied, of which the thiourea method, the thiosulfate method, the halogen method, and the lime-sulfur method are the most representative. However, these methods also have major disadvantages, mainly: the gold and silver beneficiation agent has high toxicity and complex production process, which results in high production cost.

Disclosure of Invention

The invention mainly aims to provide a gold and silver beneficiation agent, a preparation method and application thereof, and aims to provide a gold and silver beneficiation agent which is non-toxic and convenient to produce.

In order to realize the purpose, the invention provides a gold and silver beneficiation agent, which comprises the following components:

sodium ferrocyanide, urea, thiourea, sodium hydroxide, sodium carbonate, sodium sulfide and sodium sulfite.

Optionally, the gold and silver beneficiation agent comprises the following components in parts by weight:

5-10 parts of sodium ferrocyanide, 15-40 parts of urea, 8-18 parts of thiourea, 6-10 parts of sodium hydroxide, 10-20 parts of sodium carbonate, 2-5 parts of sodium sulfide and 2-5 parts of sodium sulfite.

The invention further provides a preparation method of the gold and silver beneficiation agent, which comprises the following steps:

s10, adding urea and thiourea into a closed container, heating for the first time to completely melt the materials, then continuously adding sodium hydroxide, sodium carbonate, sodium ferrocyanide, sodium sulfide and sodium sulfite into the closed container, continuously heating for the second time to completely melt the materials, and then keeping the temperature to obtain a melt;

and S20, cooling and crushing the melt to obtain the gold and silver beneficiation agent.

Optionally, in step S10, the heating temperature of the first heating is 180 ℃ to 200 ℃.

Optionally, in step S10, the heating temperature of the second heating is 800 to 900 ℃.

Optionally, in step S10, the conditions of the heat preservation are: keeping the temperature at 800-900 ℃ for 2-3 h.

Optionally, the preparation method of the gold and silver beneficiation agent further comprises:

and S30, treating the tail gas generated in the closed container.

Optionally, step S30 specifically includes:

and cooling the tail gas, and introducing the tail gas into a sodium chloride solution for reaction to obtain a mixed solution.

The invention further provides a beneficiation method, which comprises the following steps:

grinding ores containing gold and/or silver, and sequentially adding a gold and silver beneficiation agent and water to form ore pulp;

adjusting the pH value of the ore pulp to 10-11.5, continuously stirring the ore pulp for 24 hours, and carrying out solid-liquid separation to obtain a leaching solution, wherein the leaching solution contains a leaching crude product of gold and/or silver;

the gold and silver beneficiation agent is the gold and silver beneficiation agent.

Optionally, in the step of grinding the ore containing gold and/or silver, and adding a gold and silver beneficiation agent and water in sequence to form ore pulp, the mass ratio of the gold and silver beneficiation agent to the ore containing gold and/or silver is (1.5-3.9) kg: 1 t.

The technical scheme provided by the invention provides a gold and silver beneficiation agent which comprises components of sodium ferrocyanide, urea, thiourea, sodium hydroxide, sodium carbonate, sodium sulfide and sodium sulfite.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to these drawings without creative efforts.

Fig. 1 is a schematic flow chart of an embodiment of a preparation method of a gold and silver beneficiation agent provided by the present invention.

The implementation, functional features and advantages of the present invention will be further described with reference to the embodiments and the accompanying drawings.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that those whose specific conditions are not specified in the examples were conducted under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are conventional products commercially available. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, the technical solutions in the embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not be within the protection scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.

In order to solve various defects of cyanide, a large amount of research work on environment-friendly medicaments is carried out at home and abroad to find novel environment-friendly medicaments which are more effective, convenient, low-toxicity and can replace cyanide. To date, several tens of environmentally friendly leaching agents have been studied, of which the thiourea method, the thiosulfate method, the halogen method, and the lime-sulfur method are the most representative. However, these methods also have major disadvantages, mainly: the gold and silver beneficiation agent has high toxicity and complex production process, which results in high production cost.

In view of the above, the invention provides a gold and silver beneficiation agent, and aims to provide a gold and silver beneficiation agent which is non-toxic and convenient to produce. The gold and silver beneficiation agent provided by the invention comprises the following components:

sodium ferrocyanide, urea, thiourea, sodium hydroxide, sodium carbonate, sodium sulfide and sodium sulfite.

The gold and silver beneficiation agent provided by the invention comprises the components of sodium ferrocyanide, urea, thiourea, sodium hydroxide, sodium carbonate, sodium sulfide and sodium sulfite, and during beneficiation, an active component in the gold and silver beneficiation agent and gold or silver in an ore form a complex so that the gold or silver enters a solution from the ore and the leaching of the gold or silver is realized.

The sodium ferrocyanide can effectively prevent ore from caking, the toxicity of the thiourea is low, and the seven substances are used together to complex with gold or silver in the ore to form a complex during ore dressing, so that the gold and/or silver are leached out.

As a preferred embodiment of the invention, the gold and silver beneficiation agent comprises the following components in parts by mass:

5-10 parts of sodium ferrocyanide, 15-40 parts of urea, 8-18 parts of thiourea, 6-10 parts of sodium hydroxide, 10-20 parts of sodium carbonate, 2-5 parts of sodium sulfide and 2-5 parts of sodium sulfite.

Experiments show that the gold and silver beneficiation agent obtained according to the proportion has the best leaching effect on gold or silver. The gold and silver beneficiation agent has the characteristics of low toxicity, environmental protection, high leaching speed, high leaching rate, good stability and the like. In addition, experiments show that the beneficiation agent for gold and silver has excellent effects when used for gold oxide and silver oxide ores, and has good performance when used for gold and silver ores with high sulfur and high arsenic.

The present invention further provides a preparation method of the gold and silver beneficiation agent, fig. 1 is a schematic flow chart of an embodiment of the preparation method of the gold and silver beneficiation agent provided by the present invention, please refer to fig. 1, and the preparation method of the gold and silver beneficiation agent includes the following steps:

s10, adding urea and thiourea into a closed container, heating for the first time to completely melt the materials, then continuously adding sodium hydroxide, sodium carbonate, sodium ferrocyanide, sodium sulfide and sodium sulfite into the closed container, continuously heating for the second time to completely melt the materials, and then keeping the temperature to obtain a melt.

Preferably, in this step, the heating temperature of the first heating is 180 ℃ to 200 ℃. At this temperature, urea and thiourea quickly become molten.

The heating temperature of the second heating is preferably 800-900 ℃, at which the sodium hydroxide, sodium carbonate, sodium ferrocyanide, sodium sulfide and sodium sulfite can be rapidly changed into a molten state, and at the same time, the seven substances are mixed and reacted, so that the substances can be fully reacted by heat preservation, and the heat preservation condition is preferably 800-900 ℃ for 2-3 h.

It should be noted that, the order of adding urea and thiourea into the closed container is not limited in the present invention, and urea may be added first and then thiourea may also be added first, and in the embodiment of the present invention, preferably, urea and thiourea are mixed uniformly and then added into the closed container together, and the material is heated uniformly by physical mixing in advance. Similarly, sodium hydroxide, sodium carbonate, sodium ferrocyanide, sodium sulfide and sodium sulfite are preferably also mixed and then added together in a closed container.

And S20, cooling and crushing the melt to obtain the gold and silver beneficiation agent.

As the preparation of the gold and silver beneficiation agent is carried out at high temperature, gas such as NH is inevitably generated₃、 CO₂、SO₂And the gas can cause serious pollution to the environment if not directly discharged, so that in the embodiment of the invention, after the step S20, the preparation method of the gold and silver beneficiation agent further comprises the following steps:

and S30, treating the tail gas generated in the closed container.

Specifically, step S30 specifically includes:

and cooling the tail gas, and introducing the tail gas into a sodium chloride solution for reaction to obtain a mixed solution.

Introducing the tail gas into sodium chloride solution, NH₃、CO₂、SO₂Will react with sodium chloride solution to generate NH respectively₄Cl、(NH₄)₂SO₃And NaHCO₃And the mixture can be used as a fertilizer, so that the comprehensive utilization of tail gas is realized, and the sustainable development requirement is met.

The invention further provides a gold and silver beneficiation method, which comprises the following steps:

grinding ores containing gold and/or silver, and sequentially adding a gold and silver beneficiation agent and water to form ore pulp;

adjusting the pH value of the ore pulp to 10-11.5, continuously stirring the ore pulp for 24 hours, and carrying out solid-liquid separation to obtain a leaching solution, wherein the leaching solution contains a leaching crude product of gold and/or silver;

the gold and silver beneficiation agent is the gold and silver beneficiation agent.

The beneficiation method adopts the gold and silver beneficiation agent provided by the invention, and the gold or silver is leached into the solution by a leaching method to form a complex, so that the leaching effect is good.

Further, in the step of grinding the ore and sequentially adding the gold and silver beneficiation agent and the water to form the ore pulp, the mass concentration of the ore in the ore pulp is preferably 30%, and the leaching effect is best at the concentration.

Grinding ores containing gold and/or silver, wherein the grain size of the ground ores is preferably 200 meshes, the ores are favorably in full contact with a gold and silver beneficiation agent and water, the leaching rate of the gold and/or silver is improved, then, the gold and silver beneficiation agent and the water are sequentially added to form ore pulp, and the mass ratio of the gold and silver beneficiation agent to the ores is preferably (1.5-3.9) kg: 1t, the leaching effect is best under the above proportion.

The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.

Example 1

According to the weight portion, 15 portions of urea and 8 portions of thiourea are uniformly mixed, heated to 200 ℃, and completely melted, 5 portions of sodium ferrocyanide, 6 portions of sodium hydroxide, 10 portions of sodium carbonate, 2 portions of sodium sulfide and 2 portions of sodium sulfite are added, the mixture is rapidly heated to 900 ℃, kept for 3 hours, and the melt is poured out, cooled and crushed to obtain the gold and silver extracting agent. NH generated during the preparation₃、CO₂、SO₂After the exhaust gas is cooled, it is absorbed by a sodium chloride solution.

Example 2

According to the weight portion, 20 portions of urea and 12 portions of thiourea are uniformly mixed, heated to 180 ℃, and after complete melting, 5 portions of sodium ferrocyanide, 8 portions of sodium hydroxide, 15 portions of sodium carbonate, 2 portions of sodium sulfide and 2 portions of sodium sulfite are added, rapidly heated to 900 ℃, kept for 3 hours, and the melt is poured out, cooled and crushed to obtain the gold and silver extracting agent. NH generated during the preparation₃、CO₂、SO₂After the exhaust gas is cooled, it is absorbed by a sodium chloride solution.

Example 3

According to the weight portion, 30 portions of urea and 15 portions of thiourea are uniformly mixed, heated to 200 ℃, and completely melted, 8 portions of sodium ferrocyanide, 10 portions of sodium hydroxide, 15 portions of sodium carbonate, 2 portions of sodium sulfide and 2 portions of sodium sulfite are added, quickly heated to 800 ℃, kept for 3 hours, and the melt is poured out, cooled and crushed to obtain the gold and silver extracting agent. NH generated during the preparation₃、CO₂、SO₂After the exhaust gas is cooled, it is absorbed by a sodium chloride solution.

Example 4

According to the weight portion, 40 portions of urea and 18 portions of thiourea are uniformly mixed, heated to 200 ℃, and added with 8 portions of sodium ferrocyanide, 10 portions of sodium hydroxide, 20 portions of sodium carbonate, 3.5 portions of sodium sulfide and 3.5 portions of sodium sulfite after being completely melted, and then rapidly heated to 850 ℃, kept for 2-3 hours, and the melt is poured out, cooled and crushed to obtain the gold and silver extracting agent. In thatNH generated during the preparation₃、CO₂、SO₂After the exhaust gas is cooled, it is absorbed by a sodium chloride solution.

Example 5

According to the weight portion, 40 portions of urea and 18 portions of thiourea are uniformly mixed, heated to 190 ℃, and after complete melting, 10 portions of sodium ferrocyanide, 10 portions of sodium hydroxide, 20 portions of sodium carbonate, 5 portions of sodium sulfide and 5 portions of sodium sulfite are added, and then rapidly heated to 900 ℃, kept for 2-3 hours, and the melt is poured out, cooled and crushed to obtain the gold and silver extracting agent. NH generated during the preparation₃、CO₂、SO₂After the waste gas is cooled, the waste gas is absorbed by sodium chloride solution.

The gold and silver beneficiation agent and the sodium cyanide obtained in the example 1 are respectively used as beneficiation agents for beneficiation, a certain gold oxide ore in Xinjiang is used as an object, and the raw ore contains 4.29g/t of Au. Grinding the ore, and sequentially adding a gold and silver beneficiation agent and water to form ore pulp; adjusting the pH value of the ore pulp to 10, continuously stirring the ore pulp for 24 hours, and performing solid-liquid separation to obtain a leaching solution, wherein the ore dressing conditions are that the ore grinding fineness is-200 meshes and 82%, and the ore pulp concentration is 30%. The test results are shown in table 1:

TABLE 1 leaching test of gold oxide ore from Xinjiang

Test reagent	Reagent dosage (kg/t)	Grade of tailings (g/t)	Grade of noble liquid (g/t)	Leaching rate (%)
					Sodium cyanide	1.5	1.38	0.48	85.2
Example 1	1.5	1.32	0.5	84.6

As can be seen from table 1, under the same test conditions and with the same reagent amount of 1.5kg/t, the leaching rates of oxidized gold ores of the gold and silver beneficiation agent obtained in embodiment 1 of the present invention are very close to each other, and the gold and silver beneficiation agent obtained in embodiment 1 of the present invention has the advantages of no toxicity and low cost, so that the gold and silver beneficiation agent provided by the present invention can be widely applied to gold and silver beneficiation instead of sodium cyanide.

The gold and silver beneficiation agent and the sodium cyanide obtained in the example 1 are respectively used as beneficiation agents for beneficiation, a certain gold and silver-containing sulfur concentrate in Yunnan is used as a test object, the ore is a sulfur concentrate obtained by flotation of a certain polymetallic sulfide ore in Yunnan, and the ore contains 5.63g/t of Au and 52.8g/t of Ag. Before the test, the sulphur concentrate was subjected to high temperature roasting. The experimental conditions are that the grinding fineness is 95 percent of 200 meshes, the pulp concentration is 30 percent, the leaching pH is 11.5, and the leaching time is 24 hours. The test results are shown in table 2:

TABLE 2 roasting leaching test of a gold-silver-containing sulfur concentrate from Yunnan

As can be seen from Table 2, the leaching rates of the gold and silver in the gold and silver beneficiation agent are higher than those of sodium cyanide when the dosage of the gold and silver beneficiation agent is the same as that of the sodium cyanide and the dosage of the reagent is 3.9 kg/t.

By combining the results, the leaching rates of the gold and silver beneficiation agent and sodium cyanide are similar to or higher than those of the sodium cyanide under the same test conditions, and the gold and silver beneficiation agent provided by the invention has the advantages of no toxicity and low cost, so that the gold and silver beneficiation agent provided by the invention can be widely applied to gold and silver beneficiation instead of the sodium cyanide and has wide market prospects.

The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.