Preparation and application method of niobium biological extractant

Abstract

The invention relates to the technical field of recovery of niobium metal, provides a preparation method and an application method of a niobium biological extractant, and solves the problems that a method for leaching niobium metal by using an acid leaching method such as sulfuric acid in the prior art is unsafe and not environment-friendly. Comprising the following treatment steps: 1) crushing waste dried small shrimps or barnacle shells into powder to obtain a crushed material; 2) respectively carbonizing the crushed material and pencil lead powder in a muffle furnace at 120-125 DEG C for 60-70 minutes; 3) dissolving 0.009 mg / L C < l > O2 in clear water, and adding the dissolved O2 into the carbonized crushed material; (4) adding 0.72 to 0.75 mol / L of C6H8O7 into the material treated in the step (3); (5) adding the carbonized pencil lead powder with the concentration of 0.72 to 0.75 mol / L; and (6) uniformly stirring, and standing to react for 10 hours to obtain the niobium biological extractant.

Description

Technical Field

[0001] The present invention relates to the technical field of niobium metal recovery, and in particular to a preparation and application method of a niobium bioextractant. Background Art

[0002] Niobium does not appear in pure form in nature, but is combined with other elements to form minerals. It is a low-grade refractory ore and difficult to enrich to obtain concentrate. At present, niobium metallurgy at home and abroad uses extreme chemical treatment of niobium-tantalum concentrate with high-concentration hydrofluoric acid (<60%) or hydrofluoric acid-sulfuric acid mixed acid. For example, a Chinese patent document with publication number CN103361495A and publication date 2013.10.23 discloses a method for extracting niobium from Bayan Obo tailings, comprising: S1 mixing the raw material with sodium hydroxide and one of the fluxes sodium chloride, potassium chloride, potassium nitrate and sodium nitrate at a ratio of 1:0.5, and then roasting at 350-700°C for 90-200 min; S2 washing the roasted ore, filtering to obtain washed slag and washed liquid; S3 acid leaching with 3.5-8.0 mol / L hydrochloric acid, leaching temperature: 50-95°C, 40-120 min; S4 acid leaching with an inorganic acid of hydrofluoric acid and sulfuric acid with a mass fraction of 15-40% at a ratio of 2:1; S5 filtering to obtain an acid leaching solution containing niobium, and the leaching rate reaches more than 95%. For another example: Chinese patent publication number CN109837400A, with a publication date of June 4, 2019, discloses a method for extracting rare earth and niobium from niobium-rich slag, comprising: S1, mixing concentrated sulfuric acid with a mass fraction of 98% and niobium-rich slag, acidifying and decomposing at 280-300°C for 90-120 minutes, then acid leaching at 80-90°C, and then filtering out the leached slag while hot to obtain a leachate. S2, adjust the pH of the leaching solution to 0.1-0.5, and use the etheramide functional ionic liquid to have strong selectivity for rare earth at pH 0.1-0.5, and almost do not extract niobium metal ions, so as to separate rare earth metal ions from niobium metal ions; S3, use at least one of 1-alkyl-3-methylimidazolium hexafluorophosphate and 1-alkyl-3-methylimidazolium bistrifluoromethanesulfonyl imide salt to strip the loaded organic phase with water as stripping liquid to obtain a rare earth-containing solution; S4, adjust the pH of the raffinate after separating the loaded organic phase to 1.5-2.0, and age for 24-72h to hydrolyze niobium to form a precipitate rich in niobium. The leaching rates of niobium and rare earth are 80.4% and 86.2% respectively. It can be found that: the process of extracting niobium and separating niobium from rare earth by extraction method. Problems: First, in the patent CN103361495A, potassium nitrate and sodium nitrate are used as fluxes, and after mixing, they are roasted at 350-700℃ for 90-200min. Potassium nitrate is a strong oxidant. When it encounters a flammable material, it can promote the fire. When it burns and decomposes, it releases toxic nitrogen oxide gas; the toxic effects of sodium nitrate are: (1) Cardiac-increased pulse, blood pressure does not drop; (2) Lung, chest or breathing-cyanosis; (3) methemoglobinemia, carbon oxygen. Second, CN109837400A uses 98% concentrated sulfuric acid at 280-300℃ for acidification and decomposition, which is also not environmentally friendly. Summary of the invention

[0003] Therefore, in view of the above problems, the present invention provides a method for preparing and applying a niobium bio-extractant to solve the problem that the prior art "acid leaching method" using sulfuric acid or the like to leach niobium metal is unsafe and environmentally unfriendly.

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

[0005] 1) crushing the discarded shrimp skin or barnacle shell into powder to obtain a crushed product;

[0006] 2) Carbonizing the above-mentioned pulverized product and pencil lead powder in a muffle furnace at 120-125° C. for 60-70 min respectively;

[0007] 3) Dissolve 0.009 mg / L ClO2 in clean water and add it to the carbonized powder;

[0008] 4) Add 0.72-0.75 mol / L C6H8O7 to the material treated in step 3);

[0009] 5) Adding 0.72-0.75 mol / L of carbonized pencil lead powder;

[0010] 6) Stir evenly and allow to react for 10 hours to obtain a niobium bio-extractant.

[0011] Further: in step 1), the pH of the niobium bio-extractant is 6-6.1.

[0012] Further: Step 2) the specific surface area of ​​the crushed material after carbonization is BET = 2100-2200m 2 / g, the Golgi body contains 1600-1700 N-acetylglucosamine / g, which carries the charges of -NH2 and -COOH groups.

[0013] Further: after the pencil lead powder is modified by carbonization in step 5), the positive charge of the -NH2 group in the N-acetylglucosamine in the carbonized powder is shielded; the negatively charged "δ - "-COOH" appears at the middle terminal, containing 2.12 mmol / g of carboxyl group, 2.00 mmol / g of lactone group, 1.29 mmol / g of phenolic hydroxyl group and 4.49 mmol / g of carbonyl group.

[0014] Furthermore: the capacitance C of each gram of the biological niobium extractant is 205F, the electronic conductivity G is 104.6S / cm, and the electronegativity χ is less than 2.3.

[0015] Further: the negative charge capacity of the crushed material in steps 2)-5) is located in the network on the opposite side of the Golgi apparatus, and the negative charge "δ- "with the positive charge of niobium metal"δ + "The continuous back-and-forth conduction of electrons between Nb5+ receptors gradually releases energy.

[0016] A method for applying a niobium bioextractant comprises the following processing steps:

[0017] (1) Adding the above-mentioned niobium bioextractant into red mud or copper tailings or other niobium-containing minerals;

[0018] (2) At room temperature, the mixture is stirred at a speed of not less than 150 rpm for 1-1.5 hours by using a stirrer; the leaching solution is centrifuged in a centrifuge at a speed of not less than 4000 rpm for 5-10 minutes to leach niobium metal.

[0019] Further: the pH value of the red mud is 12.1-13.0, the pH value of the copper tailings is 6.3, and the outermost layer of the niobium metal element in the red mud and copper tailings containing niobium minerals is positively charged "δ + "Nb5+, electronegativity χ = 1.59; negative charge of niobium bioextractant"δ - ", forming a tight entanglement of energy and complexing into a stable ionic bond.

[0020] Furthermore: the niobium metal leaching recovery rate is above 96%.

[0021] By adopting the above technical scheme, the beneficial effects of the present invention are as follows: based on the law of "opposite charges attract each other", the present invention proposes that one of the discarded shrimp skin and barnacle shell charcoal has a negative charge-mediated extracellular electron transfer reaction mechanism after carbonization and modification. The negative charge capacitance is located in the network on the opposite side of the Golgi apparatus, and through the shuttle of electron mobility, the negative charge "δ - "with the positive charge of niobium metal"δ +"The electron conductivity between the Nb5+ receptors is constantly going back and forth, gradually releasing the energy. After being added to the red mud, it forms a complex reaction with positively charged Nb5+ and metals with electronegativity χ=1.59, and is stirred for 1-1.5h. The solid-liquid separation forms an ionic bond and stabilizes, which is the application of the law of "opposite charges attract". The advantages of the present invention are: first, the shrimp skin and barnacle shell charcoal niobium biochar extractant has the superior function of "opposite charges attract" specificity for specific niobium metal "Nb5+" during the adsorption process, and a niobium recovery rate of more than 96% can be achieved in 1-1.5h; at the same time, it has stable compatibility with the pH value of the mineral, is not affected or disturbed by the pH value, and does not require roasting The extraction of niobium can be completed with additional conditions such as strong acid and strong alkali. Secondly, the shrimp skin and barnacle shell charcoal niobium biological extractant is made from one of the natural substances, shrimp skin and barnacle shell charcoal, which is made through carbonization and modification. In addition to the function of extracting niobium metal, it is also praised by the world biomedical community as the "sixth element of life". The pencil lead powder is grafted onto the macromolecular chain of the natural substance. In addition to the function of extracting niobium metal, it can effectively remove organic pollutants floating in the air, heavy metal ions and other pollution sources, and can also improve the quality of the environment, which is green and environmentally friendly. Thirdly, the shrimp skin and barnacle shell charcoal niobium biological extractant uses natural organisms (shrimp skin and barnacle shells) as green raw materials, which are made through carbonization and modification. The raw material price is low, the production is simple and the cost is low. DETAILED DESCRIPTION

[0022] Embodiment 1

[0023] A method for preparing a niobium bioextractant comprises the following steps:

[0024] 1) crushing the discarded dried shrimp into powder;

[0025] 2) The above-mentioned pulverized product and 0.72 mol / L pencil lead powder were carbonized in a muffle furnace at 120°C for 60 min respectively;

[0026] 3) Dissolve 0.009 mg / L ClO2 in clean water and add it to the carbonized powder;

[0027] 4) Add 0.72 mol / L C6H8O7 to the material treated in step 3);

[0028] 5) Add 0.72 mol / L of carbonized pencil lead powder;

[0029] 6) Stir evenly and allow to react for 10 hours to obtain a niobium bio-extractant.

[0030] A method for applying a niobium bioextractant, comprising the following steps:

[0031] 1) Add the above niobium bioextractant into red mud with a pH value of 12.1 without adjusting the pH value;

[0032] 2) At room temperature, the mixture is stirred at a speed of not less than 150 rpm for 1 hour by a stirrer; the leaching solution is centrifuged in a centrifuge at a speed of not less than 4000 rpm for 5 minutes to leach niobium metal, and the niobium leaching recovery rate is 98.1%.

[0033] Embodiment 2

[0034] A method for preparing a niobium bioextractant comprises the following steps:

[0035] 1) crushing the discarded barnacle shells into powder;

[0036] 2) The above-mentioned pulverized product and 0.72 mol / L pencil lead powder were carbonized in a muffle furnace at 120°C for 60 min respectively;

[0037] 3) Dissolve 0.009 mg / L ClO2 in clean water and add it to the carbonized powder;

[0038] 4) Add 0.72 mol / L C6H8O7 to the material treated in step 3);

[0039] 5) Add 0.72 mol / L of carbonized pencil lead powder;

[0040] 6) Stir evenly and allow to react for 10 hours to obtain a niobium bio-extractant.

[0041] A method for applying a niobium bioextractant, comprising the following steps:

[0042] 1) Add the above niobium bioextractant into red mud with a pH value of 12.5 without adjusting the pH value;

[0043] 2) At room temperature, agitating the mixture with a stirrer at a speed of not less than 150 rpm for 1 hour; centrifuging the leaching solution in a centrifuge at a speed of not less than 4000 rpm for 5 minutes to leach niobium metal, and the niobium leaching recovery rate was 99.1%.

[0044] Embodiment 3

[0045] A method for preparing a niobium bioextractant comprises the following steps:

[0046] 1) crushing the discarded dried shrimp into powder;

[0047] 2) The above-mentioned pulverized product and 0.75 mol / L pencil lead powder were carbonized in a muffle furnace at 120°C for 60 min respectively;

[0048] 3) Dissolve 0.009 mg / L ClO2 in clean water and add it to the carbonized powder;

[0049] 4) Add 0.75 mol / L C6H8O7 to the material treated in step 3);

[0050] 5) Add 0.72 mol / L of carbonized pencil lead powder;

[0051] 6) Stir evenly and allow to react for 10 hours to obtain a niobium bio-extractant.

[0052] A method for applying a niobium bioextractant, comprising the following steps:

[0053] 1) Add the niobium bioextractant to the copper tailings (pH 6.3) without adjusting the pH value;

[0054] 2) Stirring for 1.5 hours, taking out and separating in a laboratory centrifuge, the niobium leaching recovery rate is 97.9%.

[0055] Embodiment 4

[0056] A method for preparing a niobium bioextractant comprises the following steps:

[0057] 1) Grinding the discarded shrimp skins and barnacle shells into powder;

[0058] 2) The above-mentioned pulverized product and 0.73 mol / L pencil lead powder were carbonized in a muffle furnace at 120°C for 60 min respectively;

[0059] 3) Dissolve 0.009 mg / L ClO2 in clean water and add it to the carbonized powder;

[0060] 4) Add 0.73 mol / L C6H8O7 to the material treated in step 3);

[0061] 5) Add 0.73 mol / L of carbonized pencil lead powder;

[0062] 6) Stir evenly and allow to react for 10 hours to obtain a niobium bio-extractant.

[0063] A method for applying a niobium bioextractant, comprising the following steps:

[0064] 1) Add the above niobium bio-extractant into copper tailings (pH 6.3) without adjusting the pH value;

[0065] 2) Stirring for 1-1.5 hours, then taking out and separating in a laboratory centrifuge, the niobium leaching recovery rate is 98%.

[0066] 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 niobium bioextractant, characterized in that: The processing steps include: 1) crushing the discarded shrimp skin or barnacle shell into powder to obtain a crushed product; 2) Carbonizing the above-mentioned pulverized product and pencil lead powder in a muffle furnace at 120-125° C. for 60-70 min respectively; 3) Dissolve 0.009 mg / L ClO2 in clean water and add it to the carbonized powder; 4) Add 0.72-0.75 mol / L C6H8O7 to the material treated in step 3); 5) Adding 0.72-0.75 mol / L of carbonized pencil lead powder; 6) Stir evenly and allow to react for 10 hours to obtain a niobium bio-extractant.

2. The method for preparing a niobium bioextractant according to claim 1, characterized in that: Step 1) The pH of the niobium bio-extractant is 6-6.

1.

3. The method for preparing a niobium bioextractant according to claim 1, characterized in that: Step 2) Specific surface area of ​​the crushed material after carbonization BET = 2100-2200m 2 / g, the Golgi body contains 1600-1700 N-acetylglucosamine / g, which carries the charges of -NH2 and -COOH groups.

4. The method for preparing a niobium bioextractant according to claim 1, characterized in that: After the pencil lead powder is modified by carbonization in step 5), the positive charge of the -NH2 group in the N-acetylglucosamine in the carbonized powder is shielded; the negatively charged "δ - "-COOH" appears at the middle end, containing 2.12 mmol / g carboxyl group, 2.00 mmol / g lactone group, 1.29 mmol / g phenolic hydroxyl group and 4.49 mmol / g carbonyl group.

5. The method for preparing a niobium bioextractant according to claim 1, characterized in that The electric capacity of each gram of the biological niobium extractant is C=205F, the electronic conductivity is G=104.6S / cm, and the electronegativity is χ<2.

3.

6. The method for preparing a niobium bioextractant according to claim 1, characterized in that: The negative charge capacity of the crushed material in steps 2)-5) is located in the network on the opposite side of the Golgi apparatus, and the negative charge "δ" of the modified niobium bioextractant is transferred to the negative charge capacity of the niobium bioextractant by the shuttle of electron mobility. - "with positive charge of niobium metal"δ + "The continuous back-and-forth conduction of electrons between Nb5+ receptors gradually releases energy.

7. A method for applying a niobium bioextractant, characterized in that: The processing steps include: (1) Adding the niobium bioextractant according to any one of claims 1 to 6 into red mud or copper tailings or other niobium-containing minerals; (2) At room temperature, the mixture is stirred at a speed of not less than 150 rpm for 1-1.5 hours by using a stirrer; the leaching solution is centrifuged in a centrifuge at a speed of not less than 4000 rpm for 5-10 minutes to leach niobium metal.

8. The method for using a niobium bioextractant according to claim 7, characterized in that: The pH value of the red mud is 12.1-13.0, the pH value of the copper tailings is 6.3, and the outermost layer of the niobium metal element in the red mud and copper tailings containing niobium minerals is positively charged "δ + "Nb5+, electronegativity χ = 1.59; negative charge of niobium bioextractant"δ - ", forming a tight entanglement of energy and complexing into a stable ionic bond.

9. The method for using a niobium bioextractant according to claim 7, characterized in that: The niobium metal leaching recovery rate is above 96%.