Preparation and application method of vanadium biochar extracting agent

Abstract

The invention relates to the technical field of vanadium extracting agents, provides a preparation and application method of a vanadium biochar extracting agent, and solves the problems that a vanadium extracting method in the prior art is unsafe and not environmentally friendly. Comprising the following treatment steps: 1) crushing crab shells or tidal worm shells into powder through a crusher, and carbonizing in a muffle furnace at 120-130 DEG C for 50-60 minutes; 2) dissolving 0.008-0.009 mg / L C < l > O2 in clear water, and then adding the dissolved O2; (3) adding 0.71 to 0.75 mol / L of C6H8O7 into the mixed solution; (4) adding 0.71 to 0.75 mol / L of PEO (Polyethylene Oxide) or PEG (Polyethylene Glycol); and 5) uniformly stirring, and standing to react for 8 hours to prepare the vanadium biochar extracting agent.

Description

Technical Field

[0001] The invention relates to the technical field of vanadium extractants, and in particular to a preparation and application method of a vanadium biochar extractant. Background Art

[0002] Vanadium is an important rare metal with a wide range of uses, especially in the steelmaking industry. Adding a few percent of vanadium to steel can greatly increase the elasticity and strength of the steel, and it has excellent wear resistance and burst resistance. It is both resistant to high temperatures and extremely cold. Therefore, vanadium is often used in the automotive, aviation, railway, electronic technology, defense industry and other sectors. In addition, vanadium oxide has become one of the best catalysts in the chemical industry. At present, the vanadium extraction process used to produce vanadium-containing materials mainly involves leaching vanadium metal from chemical agents such as sulfuric acid and pyrolysis. The two processes are complicated, the cost is increased, the vanadium recovery rate is significantly reduced, and the economic benefits are poor. For example: A Chinese patent document with publication number CN108866354B and publication date 2020.12.4 discloses a method for efficiently extracting vanadium from vanadium-containing ores, comprising: S1 pretreatment: first crushing the vanadium-containing clay ore to a particle size of less than 1 cm, then adding it to a ball mill, and then adding a 28% by mass sulfuric acid solution to the ball mill at a solid-liquid mass ratio of 1:1.3 for ball milling to obtain an acidic mixed material with a particle size of less than 0.15 mm; ball milling to a particle size of less than 0.15 mm; During the grinding process, a sulfuric acid solution with a mass percentage of 15 to 30% is added to the ball mill according to a solid-liquid mass ratio of 1:1 to 1.2; S2 leaching: hydrogen peroxide or potassium permanganate with a mass ratio of 1 to 2:50 is added to the above acidic mixed material according to a mass ratio of 50:2.4, and then reacted at 68°C for 4 hours; S3, ion exchange: a strongly alkaline macroporous anion exchange resin is used to adsorb the vanadium-containing leaching solution, and then a 9% by mass percentage of NaOH and a 4.5% by mass percentage of NaC l is used for desorption to prepare a vanadium-containing eluent; S4, vanadium precipitation: ammonium chloride is added to the above vanadium-containing eluent for vanadium precipitation, and ammonium metavanadate precipitate is prepared by filtration and separation; ammonium chloride is added to the vanadium-containing eluent according to a molar ratio of vanadate to ammonium chloride of 1:1.4-1.5 for natural crystallization, and the obtained natural crystal product is washed with an ammonium chloride aqueous solution with a mass concentration of 3-4%; S5, post-treatment: the ammonium metavanadate precipitate prepared above is calcined to decompose and obtain vanadium pentoxide. For another example, a Chinese patent document with publication number CN105907912A and publication date 2016.08.31 discloses a vanadium extraction method, comprising: S1, charging a mixture containing a vanadium-containing raw material and a reducing agent powder into a reduction reactor for reaction to obtain a metallized vanadium-containing material; wherein the reaction temperature is in the range of 1000 to 1066° C., and the reaction time is 10 to 18 hours; S2, sending the metallized vanadium-containing material to an electric furnace for melting treatment to obtain molten iron and vanadium-containing slag, and the vanadium-containing slag is used for vanadium extraction.The existing problems are as follows: First, the patent CN108866354B uses highly toxic agents such as 28% sulfuric acid and hydrogen peroxide or potassium permanganate with a mass ratio of 1 to 2:50 to adsorb vanadium-containing minerals, and uses 9% NaOH and 4.5% NaCl to desorb, which is extremely environmentally unfriendly; second, the patent CN105907912A uses a pyrometallurgical method at a temperature of 1000 to 1066°C and a reaction time of 10 to 18 hours for melting treatment, which is both energy-intensive and environmentally unfriendly. Summary of the invention

[0003] Therefore, in view of the above problems, the present invention provides a method for preparing and applying a vanadium biochar extractant to solve the problems that the vanadium extraction method in the prior art is unsafe and not environmentally friendly.

[0004] To achieve the above object, the present invention adopts the following technical scheme: a method for preparing a vanadium biochar extractant, comprising the following processing steps:

[0005] 1) The crab shell or woodlice shell is crushed into powder by a crusher and carbonized in a muffle furnace at 120-130°C for 50-60 minutes;

[0006] 2) Dissolve 0.008-0.009 mg / L ClO2 in clean water and then add;

[0007] 3) Add 0.71-0.75 mol / L C6H8O7;

[0008] 4) Add 0.71-0.75 mol / L PEO or PEG;

[0009] 5) Stir evenly and allow to react for 8 hours to obtain a vanadium biochar extractant.

[0010] Furthermore: the pH of the vanadium biochar extractant is 5.8-6.2.

[0011] Further: the specific surface area of ​​the crab shell or woodlice shell after carbonization is BET=1382m 2 / g, the endoplasmic reticulum contains 1300 amino acid monosaccharides / g, with positive and negative charges of -NH2 and -COOH.

[0012] Further: after the PEO or PEG modification in step (4), the positive charge of the -NH2 group in the amino acid monosaccharide is shielded; the negatively charged "δ - "-COOH appears at the middle end, and the content "δ - ”385m 2 / g, capacitance C = 133.1F / g, electron mobility μe = 19.2mA / cm 2 , electronegativity χ = 2.3.

[0013] Further: the negative charge capacitance of step (1) is located at the physical connection site between the endoplasmic reticulum ER and the mitochondrial outer membrane OMM, and the negative charge "δ - "With the positive charge of vanadium metal"δ + "Electrons are transferred back and forth between V+5 receptors.

[0014] A method for applying a vanadium biochar extractant comprises the following processing steps:

[0015] (1) adding the above-mentioned vanadium biochar extractant to other vanadium-containing minerals in red mud with a pH value of 12.1-13.0;

[0016] (2) using a stirrer to stir at a speed of not less than 150 rpm for 1-1.3 hours at room temperature; and centrifuging in a centrifuge to leach vanadium metal, wherein the speed of the centrifuge is not less than 4000 rpm, and the separation treatment is performed for 5-10 minutes.

[0017] Further: in step (2), when the vanadium bio-extractant is added to red mud or other vanadium-containing minerals and stirred, in the red mud or other vanadium-containing minerals, the vanadium nucleus electrons are positively charged "δ + "V+5, electronegativity χ=1.63; negative charge of vanadium extractant"δ - "It is tightly entangled with energy to form an attractive complex reaction; after stirring for 1-1.3 hours in step (2), a stable ionic bond is formed, and after solid-liquid separation, the vanadium leaching recovery rate is more than 96.4%.

[0018] By adopting the above technical solution, the beneficial effects of the present invention are:

[0019] The preparation and application method of the vanadium biochar extractant of the present invention is proposed based on the mechanism of "opposite charges attract each other". The vanadium biochar extractant of crab shell and woodworm shell modified with either PEO or PEG has a negative charge mediated extracellular electron transfer reaction mechanism after carbonization and modification: the functional group negative charge δ - and electron mobility, the negative charge capacity is located at the physical connection site between the endoplasmic reticulum (ER) and the mitochondrial outer membrane (OMM), and the negative charge "δ" of the vanadium bioextractant is transferred to the vanadium bioextractant by the shuttle of electron mobility. - " and the positive charge of vanadium metal "δ +”V+5 to carry out electron transfer back and forth, form a complex reaction, and become an ionic bond to stabilize, completing the leaching of vanadium metal. This is the application of the law of "opposite charges attract each other". The advantages of the present invention are: first, the crab shell and woodlice shell vanadium biochar extractor has the superior function of "opposite charges attract each other" specific to the specific vanadium metal "V+5" during the adsorption process, and a vanadium recovery rate of more than 96.4% can be achieved in 1-1.3 hours; at the same time, it has stable compatibility with the pH value of the mineral, and is not affected or disturbed by the high or low pH value. Additional conditions such as roasting or strong acid and alkali are required to complete the extraction of vanadium. Second, the vanadium bio-extractor can be extracted from any one of crab shells or lobster shells. The main components are: amino acid monosaccharides, which are praised as the "sixth element of life" by the world's biomedical community. One of PEO or PEG is grafted onto the macromolecular chain of this natural substance. In addition to achieving the function of extracting vanadium, it also helps to improve the basis of human life-protein benefits. It is accepted by cutting-edge medical science applications and is green and environmentally friendly. Third, the preparation of crab shell and woodlice shell vanadium bio-extractors is simple and low-cost. DETAILED DESCRIPTION

[0020] Embodiment 1

[0021] A method for preparing a vanadium biochar extractant comprises the following steps:

[0022] 1) The crab shells were crushed into powder and then carbonized in a muffle furnace at 120°C for 50 min;

[0023] 2) Dissolve 0.008 mg / LC 102 in clean water and then add;

[0024] 3) Add 0.71 mol / L C6H8O7;

[0025] 4) Add 0.71 mol / L PEO;

[0026] 5) Stir evenly and allow to react for 8 hours to obtain a vanadium biochar extractant.

[0027] The method for applying the vanadium biochar extractant comprises the following processing steps:

[0028] 1) Put the vanadium biochar extractant into red mud (pH value is 12.1) without adjusting the pH value, and stir for 1 hour; 2) Take it out and separate it in a laboratory centrifuge, and the vanadium leaching recovery rate is 96.4%.

[0029] Embodiment 2

[0030] A method for preparing a vanadium biochar extractant comprises the following steps:

[0031] 1) After the woodlice shells are crushed into powder, they are carbonized in a muffle furnace at 120°C for 50 min;

[0032] 2) Dissolve 0.009 mg / L ClO2 in clean water and then add;

[0033] 3) Add 0.72 mol / L C6H8O7;

[0034] 4) Add 0.72 mol / L PEG;

[0035] 5) Stir evenly and allow to react for 8 hours to obtain a vanadium biochar extractant.

[0036] The method for applying the vanadium biochar extractant comprises the following processing steps:

[0037] 1) Add vanadium extractant into red mud (pH value is 12.5) without adjusting pH value, and stir for 1.2 hours;

[0038] 2) Take out and separate in laboratory centrifuge, the vanadium leaching recovery rate is 97.5%.

[0039] Embodiment 3

[0040] A method for preparing a vanadium biochar extractant comprises the following steps:

[0041] 1) The crab shells were crushed into powder and then carbonized in a muffle furnace at 120°C for 50 min;

[0042] 2) Dissolve 0.009 mg / L ClO2 in clean water and then add;

[0043] 3) Add 0.72 mol / L C6H8O7;

[0044] 4) Add 0.73 mol / L PEO;

[0045] 5) Stir evenly and allow to react for 8 hours to obtain a vanadium biochar extractant.

[0046] The method for applying the vanadium biochar extractant comprises the following processing steps:

[0047] 1) Add the vanadium extractant into the red mud (pH value is 13.0) without adjusting the pH value and stir for 1.3 hours;

[0048] 2) Take out and separate in laboratory centrifuge, the vanadium leaching recovery rate is 97.9%.

[0049] Although the present invention has been specifically shown and described in conjunction with the preferred embodiments, it should be understood by those skilled in the art that various changes may be made to the present invention in form and details without departing from the spirit and scope of the present invention as defined by the appended claims, all of which are within the scope of protection of the present invention.

Claims

1. A method for preparing a vanadium biochar extractant, characterized in that: The processing steps include: 1) The crab shell or woodlice shell is crushed into powder by a crusher and carbonized in a muffle furnace at 120-130°C for 50-60 minutes; 2) Dissolve 0.008-0.009 mg / L ClO2 in clean water and then add; 3) Add 0.71-0.75 mol / L C6H8O7; 4) Add 0.71-0.75 mol / L PEO or PEG; 5) Stir evenly and allow to react for 8 hours to obtain a vanadium biochar extractant.

2. The method for preparing a vanadium biochar extractant according to claim 1, characterized in that: The pH of the vanadium biochar extractant is 5.8-6.

2.

3. The method for preparing a vanadium biochar extractant according to claim 1, characterized in that: The specific surface area of ​​the crab shell or woodlice shell after carbonization is BET=1382m 2 / g, the endoplasmic reticulum contains 1300 amino acid monosaccharides / g, with positive and negative charges of -NH2 and -COOH.

4. The method for preparing a vanadium biochar extractant according to claim 1, characterized in that: After PEO or PEG modification in step (4), the positive charge of the -NH2 group in the amino acid monosaccharide is shielded; the negatively charged "δ - "-COOH appears at the middle end, and the content is "δ - ”385m 2 / g, capacitance C = 133.1F / g, electron mobility μe = 19.2mA / cm 2 , electronegativity χ = 2.

3.

5. The method for preparing a vanadium biochar extractant according to claim 1, characterized in that: The negative charge capacitance of step (1) is located at the physical connection site between the endoplasmic reticulum ER and the mitochondrial outer membrane OMM, and the negative charge capacitance of the crab shell or woodlice shell vanadium bioextractor "δ - "with positive charge of vanadium metal"δ + "Electrons are transferred back and forth between V+5 receptors.

6. The method for using a vanadium biochar extractant according to claim 1, characterized in that: The processing steps include: (1) Adding a vanadium biochar extractant according to any one of claims 1 to 5 into other vanadium-containing minerals in red mud having a pH value of 12.1-13.0; (2) using a stirrer to stir at a speed of not less than 150 rpm for 1-1.3 hours at room temperature; and centrifuging in a centrifuge to leach vanadium metal, wherein the speed of the centrifuge is not less than 4000 rpm, and the separation treatment is performed for 5-10 minutes.

7. The method for using a vanadium biochar extractant according to claim 6, characterized in that: Step (2) When the vanadium bio-extractant is added to red mud or other vanadium-containing minerals and stirred, the vanadium nucleus electrons in the red mud or other vanadium-containing minerals are positively charged. + "V+5, electronegativity χ=1.63; negative charge of vanadium extractant"δ - "It is tightly entangled with energy to form an attractive complex reaction; after stirring for 1-1.3 hours in step (2), a stable ionic bond is formed, and after solid-liquid separation, the vanadium leaching recovery rate is more than 96.4%.