Rhenium extracting agent of low-carbon graphite powder modified straw carbon as well as preparation method and application of rhenium extracting agent

Abstract

The invention relates to the technical field of metallurgy of rare metals, provides a rhenium extracting agent of low-carbon graphite powder modified straw carbon as well as a preparation method and application thereof, and solves the problem of high pollution caused by extracting rhenium through high-temperature roasting after mixing and fine grinding sulfuric acid or high-power alkali in the prior art. Comprising the following raw materials: waste crop straws, low-carbon graphite powder and CF3SO3H. Wherein the waste crop straw is powdery, and the waste crop straw is sorghum straw or corn straw; the preparation method of the rhenium extracting agent comprises the following steps: S1, taking waste crop straws and low-carbon graphite powder, feeding the waste crop straws and the low-carbon graphite powder into a muffle furnace, and respectively carbonizing the waste crop straws and the low-carbon graphite powder at 300 DEG C for 60 minutes; and S2, the carbonized waste crop straw is mixed with low-carbon graphite powder, waste crop straw modified by oxidized graphite powder is obtained, CF3SO3H is added, the mixture is stirred to be uniform, standing reaction is conducted for 10 h, and the rhenium extracting agent of straw carbon modified by the low-carbon graphite powder is prepared.

Description

Technical Field

[0001] This invention relates to the field of rare metal metallurgy, and in particular to a rhenium extractant for modifying straw char with low-carbon graphite powder, its preparation method, and its application. Background Technology

[0002] Rhenium is one of the rarest elements in the Earth's crust, with an estimated average abundance of one part per billion. It possesses excellent physicochemical properties and is irreplaceable in certain applications. Rhenium is one of the most refractory metals, with a melting point as high as 3180℃. It also exhibits high mechanical strength, good plasticity, and excellent mechanical stability. The production of high-performance single-crystal superalloys using rhenium plays an irreplaceable role in the development of high-temperature alloys for aerospace engines, making it a strategic metal vital to national industrial production and technological development. However, rhenium resources are extremely limited, and independent mineral formation is rare in nature. Therefore, the separation, enrichment, and recovery of rhenium have become a research hotspot.

[0003] In China, the main methods for extracting and recovering rhenium from rhenium-bearing ores include pyrochemical roasting and chemical treatment, which are the most traditional and primary methods. Chinese Patent Publication No. CN102628111A discloses a method for extracting rhenium from rhenium-rich concentrate, comprising the following steps: S1, mixing and finely grinding the rhenium-rich concentrate with 0.5-3 times its weight of quicklime, and roasting it at 400℃~900℃ for 2-8 hours with oxygen-enriched air at a pressure of 0.2Mpa-0.5Mpa; S2, adding ammonium carbonate (2-3 times its weight of calcium) as a purification agent, and performing purification for 0.5-2 hours to address the high calcium content of the quicklime. However, this method uses 0.5-3 times the amount of rhenium ore mixed with quicklime, finely ground, and then roasted at 400℃~900℃ for 2-8 hours. The amount of quicklime used is large, and a large amount of dust and waste residue are generated during the high-temperature roasting process, which seriously pollutes the environment. At the same time, ammonium carbonate, a toxic alkaline agent with 2-3 times the mass of calcium, is used as a purification agent. The amount of ammonium carbonate used is large, and ammonia gas is generated during its decomposition. Ammonia gas is a toxic gas that will harm the environment and human health, which also seriously pollutes the environment.

[0004] Chinese Patent Publication No. CN108611496A discloses a method for extracting rhenium from copper smelting waste acid, comprising the following steps: S1, filling an exchange column with macroporous anion exchange resin, and then converting it with 5% dilute sulfuric acid for 0.8-1 hours; S2, preparing 7% ammonia water and desorbing it for 1-2 hours; the desorbed liquid is concentrated by evaporation and cooled to crystallize to obtain ammonium rheniumate crystals. However, this method uses 5% dilute sulfuric acid for 0.8-1 hours of conversion and 7% ammonia water for 1-2 hours of desorption. Sulfuric acid is a strong acid, and its use may generate acidic wastewater, causing pollution to water bodies and soil; the volatilization of ammonia water will produce ammonia gas, which is also harmful to the environment and human health. Summary of the Invention

[0005] Therefore, in view of the above problems, the present invention provides a rhenium extractant for straw char modified with low-carbon graphite powder, its preparation method and application, which solves the problem of high pollution caused by the prior art of extracting rhenium by mixing sulfuric acid or high-concentration alkali, grinding and then roasting at high temperature.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A rhenium extractant for modifying straw char with low-carbon graphite powder, comprising the following raw materials: waste crop straw, low-carbon graphite powder, and CF3SO3H; The waste crop straw is in powder form, and the waste crop straw is sorghum stalks or corn stalks.

[0007] The concentration of CF3SO3H is 0.19 mol / L-0.21 mol / L.

[0008] The preparation method of the rhenium extractant of low-carbon graphite powder modified straw charcoal described above includes the following steps: S1. Take waste crop straw and low-carbon graphite powder by weight, put them into a muffle furnace, and carbonize them at 300℃ for 60 minutes respectively. S2. The carbonized waste crop straw is mixed with low-carbon graphite powder to obtain waste crop straw modified with oxidized graphite powder. Then, CF3SO3H is added according to the weight parts, stirred evenly, and allowed to stand for 10 hours to obtain the rhenium extractant of straw carbon modified with low-carbon graphite powder.

[0009] Furthermore, in step S1, the density of the negative charge of the carbonized waste crop straw is -0.1 to -0.5 C / m³. 2 .

[0010] Furthermore, in step S2, the waste crop straw modified with graphite oxide powder has the structural formula O=CH-COOH, forming hydroxide ions -O - Its negative charge density is 0.8-10 C / m³. 2 sp of oxygen atom 3 The hybrid orbital overlaps with one orbital of another atom to form a σ bond, exhibiting nucleophilicity to positive charges, with a capacitance of C = 386 F / g and an electronegativity χ < 2.3.

[0011] The application of the rhenium extractant obtained by the above-described method for preparing rhenium extractant from straw charcoal modified with low-carbon graphite powder includes the following steps: I. The rhenium extractant of the straw char modified with the low-carbon graphite powder is added to copper tailings or rhenium-containing minerals and stirred for 1-1.5 hours to obtain the first mixture; II. The first mixture is centrifuged to separate the solid and liquid phases, and then leached rhenium metal is obtained.

[0012] Furthermore, the leaching recovery rate of the rhenium metal is ≥96%.

[0013] Furthermore, in step I, the stirring process is carried out in a stirrer at a speed of ≥150 rpm.

[0014] Furthermore, in step II, the centrifugation speed is ≥4000 rpm and the time is 5-10 min.

[0015] Furthermore, when the rhenium extractant derived from straw char modified with low-carbon graphite powder is applied to copper tailings or rhenium-containing minerals, Re 3+ Or Re 7+ To -COO - -O - -SO3 - Electrostatic attraction occurs, and the substance is adsorbed in the solution by Coulomb forces. The specific process is as follows: Re n+ +n(-SO3 − → (-SO3) n Re n+ .

[0016] Furthermore, the rhenium extractant of the straw char modified with the low-carbon graphite powder can be added to copper tailings or rhenium-containing minerals without intervention in pH and temperature.

[0017] By adopting the aforementioned technical solution, the beneficial effects of the present invention are as follows: The rhenium extractant for low-carbon graphite powder-modified straw char provided in this technical solution is based on the "opposite charge attraction" mechanism: after modification with graphite powder, the straw char becomes negatively charged hydroxide ions (-O). - ), with a charge density of 0.8-10 C / m, and composed of sp atoms of oxygen atoms. 3 Hybrid orbitals overlap with one orbital of another atom to form a σ bond, exhibiting positively charged nucleophilicity. When applied to copper tailings or other rhenium-containing minerals, the rhenium ion (Re...)... 3+ Or Re 7+ ) to -COO - -O - -SO3 - Electrostatic attraction occurs, and the substance is adsorbed in the solution by Coulomb forces. The specific process is as follows: Re n+ +n(-SO3 − → (-SO3) n Re n+ This is an application of the law that "opposite charges attract each other"; The advantages of this invention are as follows: First, the rhenium extractant from straw charcoal modified with low-carbon graphite powder exhibits superior specificity during adsorption due to the attraction of opposite charges, achieving a rhenium recovery rate of over 96%. Second, the negative charge of the rhenium extractant from straw charcoal modified with low-carbon graphite powder originates from natural ecological plants, and the low-carbon graphite powder used for modification is non-toxic. Due to its green, safe, and recyclable nature, it is hailed as "black gold" by the agricultural science community. Third, the raw materials are derived from waste sorghum or corn stalks, resulting in low cost and simple production. Attached Figure Description

[0018] Figure 1 This is a microscopic image of the rhenium extractant from straw charcoal modified with low-carbon graphite powder in an embodiment of the present invention. Figure 2 This is a test diagram of laboratory rhenium leaching in an embodiment of the present invention. Detailed Implementation Example 1

[0019] refer to Figures 1 to 2 A rhenium extractant for modifying straw char with low-carbon graphite powder comprises the following raw materials in parts by weight: 1 part 8g waste crop straw, 1 part 0.79mol / L low-carbon graphite powder, and 1 part 0.19mol / L CF3SO3H; The waste crop straw is in powder form, and the waste crop straw is sorghum stalks.

[0020] The preparation method of the rhenium extractant of low-carbon graphite powder modified straw charcoal described above includes the following steps: S1. Take waste crop straw and low-carbon graphite powder by weight, put them into a muffle furnace, and carbonize them at 300℃ for 60 minutes respectively. S2. The carbonized waste crop straw is mixed with low-carbon graphite powder to obtain waste crop straw modified with oxidized graphite powder. Then, CF3SO3H is added according to the weight parts, stirred evenly, and allowed to stand for 10 hours to obtain the rhenium extractant of straw carbon modified with low-carbon graphite powder.

[0021] In step S1, the density of the negative charge of the carbonized waste crop straw is -0.1 to -0.5 C / m³. 2 .

[0022] The structural formula of waste crop straw modified with graphite oxide powder is O=CH-COOH, forming hydroxide ions -O. - Its negative charge density is 0.8-10 C / m³. 2 sp of oxygen atom 3 The hybrid orbital overlaps with one orbital of another atom to form a σ bond, exhibiting nucleophilicity to positive charges, with a capacitance of C = 386 F / g and an electronegativity χ < 2.3.

[0023] The application of the rhenium extractant obtained by the above-described method for preparing rhenium extractant from straw charcoal modified with low-carbon graphite powder includes the following steps: I. The rhenium extractant of the straw char modified with the low-carbon graphite powder is added to copper tailings or rhenium-containing minerals and stirred for 1-1.5 hours to obtain the first mixture; II. The first mixture is centrifuged to separate the solid and liquid phases, and then leached rhenium metal is obtained.

[0024] When the low-carbon graphite powder-modified straw charcoal rhenium extractant is applied to copper tailings and other rhenium-containing minerals, rhenium ions (Re) are extracted. 3+ Or Re 7+ ) to -COO - -O - -SO3 - Electrostatic attraction occurs, and the substance is adsorbed in the solution by Coulomb forces. The specific process is as follows: Re n+ +n(-SO3 − → (-SO3) n Re n+ ; The rhenium extractant of straw char modified with the low-carbon graphite powder can be added to copper tailings or rhenium-containing minerals without the need for pH and temperature intervention.

[0025] The leaching recovery rate of the rhenium metal is 96%, calculated as follows: a. The rhenium content in the original copper tailings is 0.26 mg / kg, or 0.00026 mg / g; in this embodiment, 25 grams of the original copper tailings are used, so the total rhenium content is 0.00026 mg / g × 25g = 0.0065 mg / g; b. The residual amount of rhenium tailings after extraction is 0.26 mg / kg, or 0.00026 mg / g. The residual rate of rhenium tailings after extraction is calculated as: 0.00026 mg / g ÷ 0.0065 mg / g × 100% = 4%; c. Calculate the rhenium extraction rate: (0.0065mg / g-0.00026mg / g) / 0.0065mg / g×100%=96%.

[0026] In step I, the stirring process is carried out in a stirrer at a speed of 150 rpm.

[0027] In step II, the centrifugation speed is 4000 rpm and the time is 10 min.

[0028] Example 2 The difference from Example 1 is that: a rhenium extractant for straw char modified with low-carbon graphite powder includes the following raw materials in parts by weight: 1 part 10g waste crop straw, 1 part 0.80mol / L low-carbon graphite powder, and 1 part 0.20mol / L CF3SO3H; The waste crop straw is in powder form and is corn stalk.

[0029] The rhenium metal recovery rate is 98%, calculated as follows: a. The rhenium content in the original copper tailings is 0.26 mg / kg, or 0.00026 mg / g; in this embodiment, 50 grams of original copper tailings are used, so the total rhenium content is 0.00026 mg / g × 50g = 0.013 mg / g; b. The residual amount of rhenium tailings after extraction is 0.26 mg / kg, or 0.00026 mg / g. The residual rate of rhenium tailings after extraction is calculated as: 0.00026 mg / g ÷ 0.013 mg / g × 100% = 2%; c. Calculate the rhenium extraction rate: (0.013mg / g-0.00026mg / g) / (0.013mg / g×100%=98%).

[0030] Other technical solutions are the same as in Example 1.

[0031] Example 3 The difference from Example 1 is that: a rhenium extractant for straw char modified with low-carbon graphite powder includes the following raw materials in parts by weight: 1 part 16g waste crop straw, 1 part 0.81mol / L low-carbon graphite powder, and 1 part 0.21mol / L CF3SO3H; The waste crop straw is in powder form and is corn stalk.

[0032] The rhenium metal recovery rate is 98%, calculated as follows: a. The rhenium content in the original copper tailings is 0.26 mg / kg, or 0.00026 mg / g; in this embodiment, 50 grams of original copper tailings are used, so the total rhenium content is 0.00026 mg / g × 50g = 0.013 mg / g; b. The residual amount of rhenium tailings after extraction is 0.26 mg / kg, or 0.00026 mg / g. The residual rate of rhenium tailings after extraction is calculated as: 0.00026 mg / g ÷ 0.013 mg / g × 100% = 2%; c. Calculate the rhenium extraction rate: (0.013mg / g-0.00026mg / g) / (0.013mg / g×100%=98%).

[0033] Other technical solutions are the same as in Example 1.

[0034] Although the invention has been specifically shown and described in conjunction with preferred embodiments, those skilled in the art should understand that various changes in form and detail may be made to the invention without departing from the spirit and scope of the invention as defined in the appended claims, all of which shall be within the scope of protection of the invention.

Claims

1. A rhenium extractant for modifying straw charcoal with low-carbon graphite powder, characterized in that, The raw materials include: waste crop straw, low-carbon graphite powder, and CF3SO3H; The waste crop straw is in powder form, and the waste crop straw is sorghum stalks or corn stalks.

2. The method for preparing a rhenium extractant from low-carbon graphite powder modified straw charcoal according to claim 1, characterized in that, Includes the following steps: S1. Take waste crop straw and low-carbon graphite powder by weight, put them into a muffle furnace, and carbonize them at 300℃ for 60 minutes respectively. S2. The carbonized waste crop straw is mixed with low-carbon graphite powder to obtain waste crop straw modified with oxidized graphite powder. Then, CF3SO3H is added according to the weight parts, stirred evenly, and allowed to stand for 10 hours to obtain the rhenium extractant of straw carbon modified with low-carbon graphite powder.

3. The method for preparing a rhenium extractant from low-carbon graphite powder-modified straw charcoal according to claim 2, characterized in that, In step S1, the density of the negative charge of the carbonized waste crop straw is -0.1 to -0.5 C / m³. 2 .

4. The method for preparing a rhenium extractant from low-carbon graphite powder modified straw charcoal according to claim 2, characterized in that, In step S2, the waste crop straw modified with graphite oxide powder has the structural formula O=CH-COOH, forming hydroxide ions -O - Its negative charge density is 0.8-10 C / m³. 2 sp of oxygen atom 3 The hybrid orbital overlaps with one orbital of another atom to form a σ bond, exhibiting nucleophilicity to positive charges, with a capacitance of C = 386 F / g and an electronegativity χ < 2.

3.

5. The application of the rhenium extractant for low-carbon graphite powder modified straw char prepared by the method described in claim 2, characterized in that, Includes the following steps: I. The rhenium extractant of the straw char modified with the low-carbon graphite powder is added to copper tailings or rhenium-containing minerals and stirred for 1-1.5 hours to obtain the first mixture; II. The first mixture is centrifuged to separate the solid and liquid phases, and then the leachable rhenium metal is obtained.

6. The application of the rhenium extractant for low-carbon graphite powder modified straw char prepared by the method described in claim 5, characterized in that, The leaching recovery rate of the rhenium metal is ≥96%.

7. The application of the rhenium extractant for low-carbon graphite powder modified straw char prepared by the method described in claim 5, characterized in that, In step I, the stirring process is carried out in a stirrer at a speed of ≥150 rpm.

8. The application of the rhenium extractant for low-carbon graphite powder modified straw char prepared by the method described in claim 5, characterized in that, In step II, the centrifugation speed is ≥4000 rpm and the time is 5-10 min.

9. The application of the rhenium extractant for low-carbon graphite powder modified straw char prepared by the method described in claim 5, characterized in that, When the rhenium extractant derived from straw char modified with low-carbon graphite powder is applied to copper tailings or rhenium-containing minerals, Re 3+ Or Re 7+ To -COO - -O - -SO3 - Electrostatic attraction occurs, and the substance is adsorbed in the solution by Coulomb forces. The specific process is as follows: Re n+ +n(-SO3 − → (-SO3) n Re n+ .

10. The application of the rhenium extractant for low-carbon graphite powder modified straw char prepared by the method described in claim 5, characterized in that, The rhenium extractant of the straw char modified with the low-carbon graphite powder can be added to copper tailings or rhenium-containing minerals without the need to intervene in pH and temperature.

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