A method for activating the mineral phase of rhenium-containing coal series and enriching rhenium

Abstract

The present invention belongs to the technical field of rhenium-containing treatment in coal, and specifically relates to a method for activating the mineral phase of rhenium-containing coal-based materials and enriching rhenium. Rhenium-rich coal is treated at high temperature to obtain flue gas and combustion slag; the flue gas is passed into water to obtain a water-leaching solution and water-leaching slag; the water-leaching slag is acid-dissolved and captured to obtain an acid-soluble enriched solution; the water-leaching solution and the acid-soluble enriched solution are induced to crystallize to obtain a perrhenate; the combustion slag is roasted with a natural mineral additive under a reducing atmosphere to achieve phase transformation to obtain a mixture of rhenium-rich products and residues; the mixture of rhenium-rich products and residues is crushed and sorted to obtain rhenium-rich products and residues. The present invention focuses on the phase transformation of rhenium-containing materials in coal, and efficiently extracts rhenium from coal and its associated minerals, with a rhenium yield of more than 60%. The method has the advantages of high efficiency, high rhenium yield, low cost, small amount of acid used, and green environmental protection. It realizes the clean and efficient enrichment of rhenium from coal and its associated minerals. The overall process is simple and the flow is short.

Description

Technical Field

[0001] The invention belongs to the technical field of rhenium-containing coal processing, and in particular relates to a method for activating the mineral phase of rhenium-containing coal series and enriching rhenium. Background Art

[0002] Rhenium is an extremely important rare and precious metal resource. It plays an irreplaceable role in improving the high-temperature mechanical properties of space shuttle engine turbine blades. However, its source is very limited. Its content in the earth's crust is extremely rare, and it is only enriched to a certain extent in molybdenite. Therefore, it is of great strategic value to develop new technologies for rhenium extraction to expand its source and ensure the supply of rhenium metal.

[0003] Coal and its associated coal seams are easy to adsorb rare metals such as rhenium, gallium, and germanium during the hydrothermal mineralization stage due to the organic adsorption characteristics of coal itself and the inorganic adsorption barrier effect of associated minerals, and have extremely high utilization value. However, under the existing process conditions, the wet process using only strong acid and strong alkali leaching cannot achieve the transformation of the rhenium-containing phase in coal, and it is even more difficult to achieve the effective extraction of metals such as rhenium, and the wastewater and waste residues cause serious environmental pollution. Therefore, it is urgent to develop an efficient and green method for extracting and enriching rhenium-containing substances in coal. Summary of the invention

[0004] In order to solve the problem that the extraction and enrichment process of rhenium-containing materials in coal is not environmentally friendly and inefficient, the present invention provides a method for activating the mineral phase of rhenium-containing coal series and enriching rhenium.

[0005] To achieve the above object, the present invention adopts the following technical scheme: a method for activating the mineral phase of rhenium-containing coal series and enriching rhenium, characterized by comprising the following steps:

[0006] S1. treating rhenium-rich coal at high temperature to obtain flue gas and combustion slag;

[0007] S2. passing the flue gas into water to obtain a water-immersion solution and a water-immersion residue;

[0008] S3. The water-leached residue is acid-dissolved and captured to obtain an acid-soluble enriched liquid;

[0009] S4. inducing crystallization of the water immersion solution and the acid-soluble enriched solution to obtain a perrhenate;

[0010] S5. The combustion slag is calcined with a natural mineral additive under a reducing atmosphere to achieve phase conversion to obtain a rhenium-rich product and a residue mixture;

[0011] S6. crushing and sorting the rhenium-rich product and residue mixture to obtain a rhenium-rich product and residue.

[0012] A further technical solution is that the temperature of the high temperature treatment in step S1 is 300° C. to 600° C. and the time is 0.5 to 2 hours.

[0013] A further technical solution is that the acid used for acid dissolution capture in step S3 is one or more of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid, the acid concentration is 0.01-0.1 mol / L, the acid dosage is 0.02-0.5 L / g material mass, the temperature is 50-80°C, and the acid is dissolved and then centrifuged to obtain the acid-soluble enriched liquid.

[0014] A further technical solution is that the inducer used in the induced crystallization in step S4 is one or more of potassium perrhenate, sodium perrhenate, and calcium perrhenate, the induction time is 1 to 2 hours, the amount of the inducer is 0.2 to 4 g / L of water immersion solution or acid-soluble enrichment solution, the induced crystallization reaction temperature is 60 to 90°C, the stirring speed is 60 to 120 rpm, and the stirring method is magnetic stirring or stirring with a stirring paddle.

[0015] A further technical solution is that the reducing atmosphere in step S5 is one or a combination of CO and H2.

[0016] A further technical solution is that the natural mineral additive in step S5 is one or more of pyrite, chalcopyrite and pyrrhotite, and the added amount thereof is 1.2 to 6.5 times that of the combustion slag.

[0017] A further technical solution is that the calcination temperature in step S5 is 1000-1200° C. and the calcination time is 30-60 min.

[0018] Reaction mechanism: The organic rhenium-containing phase in the rhenium-rich coal is volatilized in the form of rhenium pentoxide after combustion and collected by water leaching to obtain perrhenate. The inorganic rhenium-containing phase in the rhenium-rich coal is roasted with natural mineral additives under a reducing atmosphere and converted into a rhenium sulfide phase, which is liquid at high temperature and is easily separated from the slag phase. The rhenium-rich material is then crushed and separated.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention focuses on the phase transformation of rhenium-containing substances in coal, and efficiently extracts rhenium from coal and its associated minerals, with a rhenium yield greater than 60%. The method of the present invention has the advantages of high efficiency, high rhenium yield, low cost, low acid usage, and green environmental protection, and realizes clean and efficient enrichment of rhenium from coal and its associated minerals. The overall process is simple, the process is short, and the industrial application prospect is broad. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0023] Example 1

[0024] A method for activating the mineral phase of rhenium-containing coal series and enriching rhenium, the method comprising the following steps:

[0025] 10g of rhenium-rich coal was subjected to high-temperature treatment to obtain flue gas and combustion slag; the temperature of high-temperature treatment was 400°C and the time was 1h. The flue gas was passed into pure water to obtain a water-immersion solution and water-immersion slag. The water-immersion slag was acid-dissolved and captured to obtain an acid-soluble enriched liquid. The acid used was dilute hydrochloric acid, the acid concentration was 0.1mol / L, the acid dosage was 0.5L / g material mass, the temperature was 80°C, and the acid-soluble enriched liquid was obtained by centrifugal filtration after acid dissolution. Both the water-immersion solution and the acid-soluble enriched liquid were induced to crystallize to obtain perrhenate. The inducer used in the induced crystallization was potassium perrhenate, the induction time was 1h, the inducer dosage was 4g / L water-immersion solution or acid-soluble enriched liquid, the induced crystallization reaction temperature was 90°C, the stirring speed was 120rpm, and the stirring method was magnetic stirring. The combustion slag is roasted with a natural mineral additive under a reducing atmosphere to achieve phase transformation, thereby obtaining a mixture of a rhenium-rich product and a residue, wherein the reducing atmosphere is CO, the natural mineral additive is pyrite, the amount of which is twice that of the combustion slag, the roasting temperature is 1000° C., and the time is 30 minutes. The mixture of the rhenium-rich product and the residue is crushed and sorted to obtain a rhenium-rich product and a residue.

[0026] According to the test, in this embodiment, the rhenium recovery rate reaches 62.71%, and the proportion of the rhenium sulfide phase in the rhenium-rich product reaches 80%.

[0027] Example 2

[0028] A method for activating the mineral phase of rhenium-containing coal series and enriching rhenium, the method comprising the following steps:

[0029] 10g of rhenium-rich coal is subjected to high-temperature treatment to obtain flue gas and combustion slag; the temperature of high-temperature treatment is 500℃ and the time is 1h. The flue gas is passed into pure water to obtain a water-immersion solution and water-immersion slag, and the water-immersion slag is acid-dissolved and captured to obtain an acid-soluble enriched liquid. The acid used is dilute hydrochloric acid, the acid concentration is 0.05mol / L, the acid dosage is 0.4L / g material mass, the temperature is 70℃, and the acid-soluble enriched liquid is obtained by centrifugal filtration after acid dissolution. The water-immersion solution and the acid-soluble enriched liquid are induced to crystallize to obtain perrhenate. The inducer used in the induced crystallization is sodium perrhenate, the induction time is 1h, the inducer dosage is 2g / L water-immersion solution or acid-soluble enriched liquid, the induced crystallization reaction temperature is 80℃, the stirring speed is 90rpm, and the stirring method is magnetic stirring. The combustion slag is roasted with a natural mineral additive under a reducing atmosphere to achieve phase transformation, and a mixture of rhenium-rich products and residues is obtained. The reducing atmosphere is H2, the natural mineral additive is chalcopyrite, and its addition amount is 4 times that of the combustion slag. The roasting temperature is 1100°C and the time is 60 minutes. The mixture of rhenium-rich products and residues is crushed and sorted to obtain rhenium-rich products and residues.

[0030] According to the test, in this embodiment, the rhenium recovery rate reaches 66.52%, and the proportion of rhenium sulfide phase in the rhenium-rich product reaches 75%.

[0031] Example 3

[0032] A method for activating the mineral phase of rhenium-containing coal series and enriching rhenium, the method comprising the following steps:

[0033] 10g of rhenium-rich coal was subjected to high-temperature treatment to obtain flue gas and combustion slag; the temperature of high-temperature treatment was 600°C and the time was 1.5h. The flue gas was passed into pure water to obtain a water-immersion solution and water-immersion slag, and the water-immersion slag was acid-dissolved and captured to obtain an acid-soluble enriched liquid. The acid used was dilute hydrochloric acid, the acid concentration was 0.01mol / L, the acid dosage was 0.3L / g material mass, the temperature was 60°C, and the acid-soluble enriched liquid was obtained by centrifugal filtration after acid dissolution. The water-immersion solution and the acid-soluble enriched liquid were induced to crystallize to obtain perrhenate. The inducer used in the induced crystallization was potassium perrhenate, the induction time was 1.5h, the inducer dosage was 3g / L water-immersion solution or acid-soluble enriched liquid, the induced crystallization reaction temperature was 85°C, the stirring speed was 100rpm, and the stirring method was magnetic stirring. The combustion slag is roasted with a natural mineral additive under a reducing atmosphere to achieve phase transformation, thereby obtaining a mixture of a rhenium-rich product and a residue, wherein the reducing atmosphere is CO, the natural mineral additive is pyrite, the amount of which is 1.5 times that of the combustion slag, the roasting temperature is 1100° C., and the time is 40 minutes. The mixture of the rhenium-rich product and the residue is crushed and sorted to obtain a rhenium-rich product and a residue.

[0034] According to the test, in this embodiment, the rhenium recovery rate reaches 73.94%, and the proportion of rhenium sulfide phase in the rhenium-rich product reaches 65%.

[0035] The description of the above specification and embodiments is used to explain the protection scope of the present invention, but does not constitute a limitation on the protection scope of the present invention. Through the enlightenment of the present invention or the above embodiments, ordinary technicians in this field can obtain modifications, equivalent substitutions or other improvements to the embodiments of the present invention or part of the technical features thereof through logical analysis, reasoning or limited experiments, which should be included in the protection scope of the present invention.

Claims

1. A method for activating the mineral phase of rhenium-containing coal series and enriching rhenium, characterized in that The following steps are involved: S1. treating rhenium-rich coal at high temperature to obtain flue gas and combustion slag; S2. passing the flue gas into water to obtain a water-immersion solution and a water-immersion residue; S3. The water-leached residue is acid-dissolved and captured to obtain an acid-soluble enriched liquid; S4. inducing crystallization of the water immersion solution and the acid-soluble enriched solution to obtain a perrhenate; S5. The combustion slag is calcined with a natural mineral additive under a reducing atmosphere to achieve phase conversion to obtain a rhenium-rich product and a residue mixture; S6. crushing and sorting the rhenium-rich product and the residue mixture to obtain a rhenium-rich product and a residue; The temperature of the high temperature treatment in step S1 is 300°C to 600°C; the natural mineral additive in step S5 is one or more of pyrite, chalcopyrite, and pyrrhotite; the temperature of the roasting in step S5 is 1000 to 1200°C, and the time is 30 to 60 minutes.

2. The method for activating the mineral phase of rhenium-containing coal series and enriching rhenium according to claim 1, characterized in that: The time of high temperature treatment in step S1 is 0.5 to 2 hours.

3. The method for activating the mineral phase of rhenium-containing coal series and enriching rhenium according to claim 1, characterized in that: The acid used for acid dissolution capture in step S3 is one or more of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid, the acid concentration is 0.01-0.1 mol / L, the acid dosage is 0.02-0.5 L / g material mass, the temperature is 50-80° C., and after acid dissolution, centrifugal filtration is performed to obtain an acid-soluble enriched liquid.

4. The method for activating the mineral phase of rhenium-containing coal series and enriching rhenium according to claim 1, characterized in that: The inducing agent used in the inducing crystallization in step S4 is one or more of potassium perrhenate, sodium perrhenate, and calcium perrhenate. The induction time is 1 to 2 hours. The amount of the inducing agent is 0.2 to 4 g / L of water immersion solution or acid-soluble enrichment solution. The inducing crystallization reaction temperature is 60 to 90° C., the stirring speed is 60 to 120 rpm, and the stirring method is magnetic stirring or stirring with a stirring paddle.

5. The method for activating the mineral phase of rhenium-containing coal series and enriching rhenium according to claim 1, characterized in that: In step S5, the reducing atmosphere is one or a combination of CO and H2.

6. The method for activating the mineral phase of rhenium-containing coal series and enriching rhenium according to claim 1, characterized in that: In step S5, the amount of the natural mineral additive added is 1.2 to 6.5 times that of the combustion slag.

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