CN107638957B - Furfuryl hydroximic acid collecting agent and preparation method and application thereof - Google Patents
Furfuryl hydroximic acid collecting agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates toThe field of flotation reagents, in particular to a furfuryl hydroximic acid collecting agent, a preparation method and application thereof. The furfuryl hydroximic acid collecting agent has a molecular formula of C5H5NO3The furfuryl hydroximic acid collecting agent has strong collecting capacity on oxide ore wolframite, scheelite, ilmenite and bastnaesite, has good water solubility, can be completely dissolved in water at low temperature, is easy to add and operate, and saves the medicament cost.
Description
Technical Field
The invention relates to the field of flotation reagents, in particular to a furfuryl hydroximic acid collecting agent and a preparation method and application thereof.
Background
The hydroximic acid has good flotation effect on copper oxide ore, hematite, goethite, wolframite, tin ore, calcium iron ore, niobium iron ore, rare earth ore and the like, and the hydroximic acid or the alkali metal salt thereof can be mixed with Cu2+、Fe3+The plasma generates chelate, and for the structure of the chelate, the research considers that hydroximic acid is a complexing agent of 0, 0 type bonding atoms, cations on the surface of the ore are firstly hydrolyzed, and then the hydroximic acid is adsorbed on the surface of the ore to generate a 0, O five-membered ring complex.
Tungsten resources are one of the most important strategic resources in China, and the industrial development of the tungsten resources is related to national economic life and national defense safety. China is the largest tungsten resource country in the world and occupies nearly 62% of the tungsten resource reserves in the world, but China is also the largest tungsten resource supply country in the world and supplies about 80% of the tungsten resource reserves in the world for a long time, so that the existing tungsten resource reserves in China are seriously mismatched with the supply. Wolframite is mainly consumed in China, and the smelting process basically takes the wolframite as a raw material. However, the black tungsten resources in China are almost exhausted after the exploitation for hundreds of years. At present, the wolframine is mainly recovered by a reselection method in China, but the reselection recovery rate of the wolframine fine mud is generally below 45 percent. Generally, the loss rate of tungsten in the slime is reported to be 20%. Therefore, the strengthening of the efficient development and utilization of the tungsten black fine mud has great strategic significance.
The flotation process is generally considered to be one of the most efficient and economic extraction methods of the black tungsten fine mud, and the collecting agent is the technical core for realizing the flotation recovery of the black tungsten fine mud. The flotation collector of the black tungsten fine mud mainly comprises oleic acid, styrene phosphoric acid, benzyl arsonic acid, benzohydroxamic acid and the like, wherein the benzohydroxamic acid is most widely applied, and the defects of sensitivity to slime, weak collecting capability, poor selectivity and the like in a flotation process cannot be overcome, so that the comprehensive utilization rate of the black tungsten fine mud is low. The structure of the collecting agent is one of the key factors for determining whether the mineral can float, so that research and development of the high-efficiency flotation collecting agent with a new structure are significant for solving the problems of the flotation process and sustainable development of black tungsten resource utilization.
Disclosure of Invention
The invention aims to provide a furfuryl hydroximic acid collecting agent, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a furfuryl hydroximic acid collecting agent with a molecular formula of C5H5NO3The molecular structure is shown as formula-I,
the preparation method of the furfuryl hydroximic acid collecting agent comprises the following steps:
(1) preparing raw materials, namely taking methyl furoate, hydroxylamine hydrochloride and sodium hydroxide as raw materials, wherein the molar ratio of the three raw materials is 1.0: 1.2-1.5: 2.4-3.0;
(2) dissolving hydroxylamine hydrochloride in absolute methanol, stirring by magnetic force at a stirring speed of 600 r/min-1000 r/min, heating by an oil bath at a constant temperature of 50 ℃, adding 3 batches of sodium hydroxide in 30min, and filtering after the reaction is finished to obtain a filtrate;
(3) adding methyl furoate with a molecular structure shown as a formula-II into the filtrate obtained in the step (2), heating in an oil bath at a constant temperature of 80-110 ℃, reacting for 8-12 h, and after the reaction is finished, distilling the obtained reaction solution under reduced pressure to obtain a furfuryl hydroximic acid crude product;
(4) and (4) washing the crude furfuryl hydroximic acid product obtained in the step (3) with anhydrous ethyl acetate for 3-4 times, and filtering to obtain high-purity furfuryl hydroximic acid.
When the furfuryl hydroximic acid collecting agent is applied to wolframite flotation, the flotation process conditions are as follows: the dosage of the furfuryl hydroximic acid is 120-1200 g/t (equivalent to 40-400 mg/L), the granularity of ore is-200 meshes and accounts for 60-100%, lime, sodium hydroxide or sodium carbonate is added to adjust the pH of ore pulp to be 4-13, lead nitrate is added as an activating agent, the dosage is 10-150 g/t, the action time is 3-10 min, No. 2 oil is added as a foaming agent, the dosage is 5-30 g/t, and the action time is 1 min.
When the furfuryl hydroximic acid collecting agent is applied to scheelite flotation, the flotation process conditions are as follows: the dosage of the furfuryl hydroximic acid is 120-1200 g/t (equivalent to 40-400 mg/L), the granularity of ore is-200 meshes and accounts for 60-100%, lime, sodium hydroxide or sodium carbonate are added to adjust the pH value of ore pulp to 4-11, No. 2 oil is added as a foaming agent, the dosage is 5-30 g/t, and the action time is 1 min.
When the furfuryl hydroximic acid collecting agent is applied to flotation of ilmenite or bastnaesite, the flotation process conditions are as follows: the dosage of the furfuryl hydroximic acid is 120-1200 g/t (equivalent to 40-400 mg/L), the ore granularity is-0.074 mm and accounts for 60-100%, lime, sodium hydroxide or sodium carbonate is added to adjust the pH of the ore pulp to 4-13, No. 2 oil is added as a foaming agent, the dosage is 5-30 g/t, and the action time is 1 min.
The furfuryl hydroximic acid collecting agent has strong collecting capacity on minerals such as oxide ore wolframite, scheelite, ilmenite, bastnaesite and the like, and is suitable for collecting oresThe pH value of the flotation pulp is 4-13, and the dosage is 120-1200 g/t (equivalent to 40-400 mg/L). The furohydroxamic acid has a structure shown as a formula-I, belongs to an electron-rich system, is a furan heterocyclic organic matter, and contains O atoms with stronger electronegativity than C atoms, so that the furohydroxamic acid is more active than hydroxyoximino on a benzene ring; because the double bond exists, p-pi conjugation exists, electrons on the 2 nd position are easier to shift to a heterocyclic ring, a hydroxyoximino group is more active and is easier to combine with metal ions on the surface of a mineral, so that the adsorption of the hydroxyoximino group on mineral particles is firmer, a more stable chelate ring is formed, and the collecting capability of the hydroxyoximino group is enhanced. Can be metal atoms W of the ore surface6+、Ti4+、Cu2+、Sn2+And Ce3+The outer layer of empty track provides lone electron pairs, so that chelate is formed by bonding, the purpose of stronger collecting capacity is achieved, the method is suitable for floating refractory fine-grained oxidized ore, and the floating effect and the mineral separation index are improved. The furfuryl hydroximic acid has good water solubility, can be completely dissolved in water at low temperature, is easy to add and operate, and saves the medicament cost.
Drawings
FIG. 1 is a flow chart of the experiment for flotation of pure wolframine minerals by furfuryl hydroximic acid and other hydroximic acids.
FIG. 2 is a flow chart of the flotation experiment of bastnaesite or ilmenite monomineral with the furfuryl hydroximic acid and other hydroximic acids according to the present invention.
FIG. 3 is a flow chart of a test of the present invention for the flotation of a black tungsten slime from furfuryl hydroxamic acid (example 6).
Detailed Description
The invention is further illustrated by, but is not limited to, the following examples. All amounts and percentages in the examples refer to quality parameters unless otherwise indicated.
When the furfuryl hydroximic acid is applied to ore flotation, the main operation flow is as follows: grinding the selected ore to the required floatation granularity, then adding a regulator, a collecting agent furfuryl hydroximic acid and a foaming agent, and then re-aerating, floating and scraping bubbles to obtain the useful metal mineral.
Example 1: preparation of furfuryl hydroximic acid
Pouring 200mL of anhydrous methanol into a 500mL three-neck flask, heating by an oil bath at the constant temperature of 50 ℃, and condensing and refluxing at normal temperature; firstly, adding 8.34 parts of hydroxylamine hydrochloride into a three-neck flask, then adding 8.8 parts of sodium hydroxide in 3 batches, and reacting for 30 min; filtering the reactant to obtain a filtrate; adding methyl furoate with a structure shown in formula-II into the filtrate, heating the reaction system in a water bath at the constant temperature of 80 ℃ for 10h, and distilling the solution under reduced pressure after the reaction is finished to obtain a furoic acid hydroximic acid crude product; and washing the crude product with anhydrous ethyl acetate for 3-4 times, and filtering to obtain the high-purity furfuryl hydroximic acid. The reaction process is shown as formula-III and formula-IV.
Example 2: comparison of Furfuryhydroxamic acid flotation Performance on pure Black tungsten mineral with other hydroximic acids
The flotation test is carried out by adopting an XFG II type hanging groove type flotation machine. The feeding granularity of the pure wolframine mineral is 0.074 mm-0.038 mm. Firstly, adding 2g of pure minerals and 35mL of distilled water into a flotation tank, and stirring and mixing the slurry for 1 min; then adjusting the pH value of the ore pulp to the set values shown in the table 1 and the table 2 by using HCl or NaOH, and stirring for 2 min; then, the activator Pb (NO) is added in turn3)244mg/L, action time of 5min, collecting agent hydroximic acid, action time of 3min, foaming agent No. 2 oil of 5mg/L, action time of 1min, and finally aerating and scraping for 5 min; and after the flotation test is finished, filtering, drying and weighing the foam product, and calculating the recovery rate. The detailed test procedure and the drug regimen are shown in FIG. 1, and the test results are shown in tables 1 and 2.
TABLE 1 results of research on flotation performance test of pure mineral of wolframine nigrum with hydroximic acid (%)
Table 2 results of experimental study on flotation performance of pure wolframine mineral using amount of furfuryl hydroxamic acid (%)
Example 3: comparison of Furfuryhydroxamic acid flotation Performance on pure mineral scheelite with other hydroximic acids
The flotation test is carried out by adopting an XFG II type hanging groove type flotation machine. The feeding granularity of the pure scheelite mineral is 0.074 mm-0.038 mm. Firstly, adding 2g of pure minerals and 35mL of distilled water into a flotation tank, and stirring and mixing the slurry for 1 min; then adjusting the pH value of the ore pulp to the setting values shown in the tables 3 and 4 by using HCl or NaOH, and stirring for 2 min; then, adding a collecting agent hydroximic acid in sequence, reacting for 3min, a foaming agent No. 2 oil of 5mg/L, reacting for 1min, and finally aerating and scraping for 5 min; and after the flotation test is finished, filtering, drying and weighing the foam product, and calculating the recovery rate. The test flow and the drug formulation are shown in FIG. 2, and the test results are shown in tables 3 and 4.
TABLE 3 results of research on flotation performance test of hydroximic acid on pure mineral of scheelite (%)
TABLE 4 results of experimental study on flotation performance of pure mineral of scheelite with the amount of furfuryl hydroxamic acid (%)
Example 4 comparison of Furfurohydroxamic acid flotation Performance on fluorocarbon cerium Monomineral with other hydroximic acids
The ore feeding granularity of the fluorine-carbon-cerium single mineral is 0.074 mm-0.038 mm. Firstly, adding 2g of pure minerals and 35mL of distilled water into a flotation tank, and stirring and mixing the slurry for 1 min; then adjusting the pH value of the ore pulp to the setting values shown in the tables 5 and 6 by using HCl or NaOH, and stirring for 2 min; then, adding a collecting agent hydroximic acid in sequence, reacting for 3min, a foaming agent No. 2 oil of 5mg/L, reacting for 1min, and finally aerating and scraping for 5 min; and after the flotation test is finished, filtering, drying and weighing the foam product, and calculating the recovery rate. The detailed test procedure and drug regimen are shown in FIG. 2, and the test results are shown in tables 5 and 6.
TABLE 5 results of research on flotation performance test of hydroximic acid on fluorocarbon cerium monomineral (%)
TABLE 6 results of experimental study of the flotation properties of the amount of furfuryl hydroxamic acid on fluorocarbon cerium monominerals (%)
Example 5 comparison of Furfurohydroxamic acid with other hydroxamic acids on flotation of ilmenite Mono minerals
The feeding granularity of the ilmenite is 0.074 mm-0.038 mm. Firstly, adding 2g of pure minerals and 35mL of distilled water into a flotation tank, and stirring and mixing the slurry for 1 min; then adjusting the pH value of the ore pulp to the setting values shown in the table 7 and the table 8 by using HCl or NaOH, and stirring for 2 min; then, adding a collecting agent hydroximic acid in sequence, reacting for 3min, a foaming agent No. 2 oil of 5mg/L, reacting for 1min, and finally aerating and scraping for 5 min; and after the flotation test is finished, filtering, drying and weighing the foam product, and calculating the recovery rate. The detailed test procedure and drug regimen are shown in FIG. 2, and the test results are shown in Table 4.
TABLE 7 results of research on flotation performance test of hydroximic acid on ilmenite pure mineral (%)
Table 8 results of experimental study of the flotation properties of pure ilmenite with furfuryl hydroxamic acid amount (%)
Example 6: flotation of Jiangxi tungsten slime by furfuryl hydroximic acid
The black tungsten fine mud sample is taken from black tungsten fine mud of a certain mine in Jiangxi, and the multi-element and tungsten phase analysis of the sample are respectively shown in Table 9 and Table 10. The wolframite fine mud mainly comprises wolframite and cassiterite, the main associated minerals comprise chalcopyrite, galena, sphalerite, molybdenite and pyrite, and the main gangue minerals comprise quartz and aluminosilicateMinerals, and the like. As can be seen from Table 11 showing the particle size composition and tungsten distribution results of the black tungsten sludge, the-0.074 fraction of the black tungsten sludge accounts for 81.25%, and among them, WO of the-0.074 mm fraction3WO of the 91.94% and-0.038 mm size fraction348.41% of the raw materials, which belong to typical black tungsten fine mud.
The small closed-loop test procedure and the drug regimen are shown in FIG. 3, and the results are shown in Table 12.
TABLE 9 multielement analysis of black tungsten fine mud samples
| Element(s) | WO3 | Cu | Mo | S | Bi | Sn | P |
| Content (%) | 0.26 | 0.15 | 0.018 | 0.76 | 0.053 | 0.09 | 0.09 |
| Element(s) | Al2O3 | Pb | Zn | SiO2 | CaF2 | CaO | Fe |
| Content (%) | 8.52 | 0.15 | 0.16 | 72.50 | 0.09 | 0.85 | 4.87 |
TABLE 10 wolframium tungsten phase analysis (%)
| Phase difference | Wolframite ore | Scheelite ore | Tungsten bloom | Total tungsten |
| Content (%) | 0.223 | 0.035 | 0.002 | 0.26 |
| Occupancy (%) | 85.77 | 13.46 | 0.77 | 100.00 |
TABLE 11 Black tungsten Fine mud fraction composition and tungsten distribution (%)
| Size fraction (mm) | Yield of | WO3Grade (L) of a material | WO3Distribution ratio | WO3Cumulative distribution ratio |
| +0.074 | 18.75 | 0.11 | 8.05 | 8.05 |
| -0.074+0.038 | 35.35 | 0.32 | 43.54 | 51.59 |
| -0.038 | 45.90 | 0.28 | 48.41 | 100.00 |
| Total up to | 100.00 | 0.26 | 100.00 | —— |
TABLE 12 closed circuit test indices (%)
Claims (3)
1. The application of the furfuryl hydroximic acid collecting agent in the wolframite flotation is characterized in that the flotation process conditions are as follows: the dosage of the furfuryl hydroximic acid is 120-1200 g/t, the granularity of ore is-200 meshes and accounts for 60-100%, lime, sodium hydroxide or sodium carbonate are added to adjust the pH value of the ore pulp to 4-13, lead nitrate is added as an activating agent, the dosage is 10-150 g/t, the action time is 3-10 min, No. 2 oil is added as a foaming agent, the dosage is 5-30 g/t, and the action time is 1 min;
the molecular structure of the furfuryl hydroximic acid collecting agent is shown as a formula-I,
2. the application of the furfuryl hydroximic acid collecting agent in scheelite flotation is characterized in that the flotation process conditions are as follows: the dosage of the furfuryl hydroximic acid is 120-1200 g/t, the granularity of ore is-200 meshes and accounts for 60-100%, lime, sodium hydroxide or sodium carbonate are added to adjust the pH value of the ore pulp to 4-11, No. 2 oil is added as a foaming agent, the dosage is 5-30 g/t, and the action time is 1 min;
the molecular structure of the furfuryl hydroximic acid collecting agent is shown as a formula-I,
3. the application of the furfuryl hydroximic acid collecting agent in the flotation of ilmenite or bastnaesite is characterized in that the flotation process conditions are as follows: the dosage of the furfuryl hydroximic acid is 120-1200 g/t, the ore granularity is-0.074 mm and accounts for 60-100%, lime, sodium hydroxide or sodium carbonate are added to adjust the pH value of the ore pulp to 4-13, No. 2 oil is added as a foaming agent, the dosage is 5-30 g/t, and the action time is 1 min;
the molecular structure of the furfuryl hydroximic acid collecting agent is shown as a formula-I,
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| CN113941453B (en) * | 2021-09-30 | 2024-01-30 | 郑州大学 | Flotation method and system for ilmenite |
| CN113941452B (en) * | 2021-09-30 | 2024-01-30 | 郑州大学 | Flotation method and flotation system for micro-fine particle ilmenite |
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| CN103922968A (en) * | 2014-05-07 | 2014-07-16 | 中南大学 | Preparation method of hydroxamic acid or hydroxamic acid salt |
| CN106423574A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of aliphatics bis-hydroximic acid compound to mineral flotation |
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| CN104447409A (en) * | 2014-11-12 | 2015-03-25 | 中蓝连海设计研究院 | Synthesis method of hydroxyoximate |
| CN105170338B (en) * | 2015-08-28 | 2017-12-08 | 河南天鸿选矿科技有限公司 | A kind of non-sulfide ore mineral floating collecting agent and its preparation method and application |
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