Hydroximic acid flotation collecting agent and synthesis method and application thereof
By preparing and applying naphthylaminohydroxyoxime compounds as flotation collectors, the problem of low recovery rate of valuable metals in mineral flotation in existing technologies has been solved, especially in rare earth, cassiterite and copper oxide minerals, the recovery rate has been significantly improved.
Patent Information
- Application Number
- CN202610266479.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-05
- Publication Date
- 2026-05-12
AI Technical Summary
There are no existing technologies for the application of naphthylamine dihydroxamic acid compounds as mineral flotation collectors, especially in the enrichment and recovery of valuable metals in minerals such as rare earths, cassiterite, and copper oxide.
Naphthylaminohydroxamic acid compounds with specific structures are used as flotation collectors. Aminoaminohydroxamic acid compounds are prepared through synthetic routes S1-S4 and applied in mineral flotation processes, especially to improve the recovery rate of valuable metals in minerals such as rare earth, cassiterite and copper oxide.
It improves the flotation recovery rate of valuable metals in minerals such as rare earth, cassiterite and copper oxide, showing a significant improvement compared to the commonly used collector H2O5, especially at pH=8.
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Figure CN122006905A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of metal beneficiation technology, and relates to a hydroxyoxime acid flotation collector, its synthesis method and application, specifically the application of a hydroxyoxime acid flotation collector in the flotation and recovery of valuable metals from non-ferrous and precious metal minerals such as rare earth, cassiterite and copper oxide. Background Technology
[0002] Hydroxime acids possess biological activity. In medicine, they can be used as drugs with analgesic, anti-inflammatory, and anti-cancer effects. Especially with the increasing incidence of cancer, research on anti-cancer drugs has attracted significant attention both domestically and internationally. Related experiments have confirmed that the development and progression of malignant tumors are inseparable from the imbalance of histone deacetylation, and hydroxyxamic acid inhibitors can increase the degree of histone acetylation, thereby selectively inhibiting tumor cell proliferation. Currently, biochemists both domestically and internationally have recognized their diverse structures, high activity, and strong specificity, and are racing to develop a large number of anti-cancer drugs. The safety, biological activity against tumor cells, and mechanism of action of sialylaniline isohydroxamic acid (SAHA) were studied through oral administration or intravenous injection. It was found that it has a good inhibitory effect on tumor cell activity and proliferation, inducing apoptosis, and has relatively few toxic side effects on renal function and blood cells. The anticancer properties of synthesized tin furfural isohydroxamic acid complexes were studied, and the results showed that both phenyl and n-butylfurfural isohydroxamic acid complexes exhibited good anticancer effects. In metallurgy, hydroxamic acid compounds can serve as highly selective extractants. Furthermore, a novel calix-shaped hydroxamic acid was synthesized, which can be used for the trace determination, sequential separation, and liquid-liquid extraction of Cr(III), Mo(VI), and W(VI). Experiments showed that in chloroform solvent with a large number of cations and anions, Cr(III), Mo(VI), and W(VI) could be extracted at pH 4.5 and hydrochloric acid concentrations of 1.5 mol / L and 6.0 mol / L, respectively.
[0003] Hydroxime acids also possess stable chelating properties and can be used as flocculants and precipitants in wastewater treatment. Wang Bi et al. synthesized polyhydroxyxamic acid from composite polyacrylamide, hydroxylamine hydrochloride, and sodium hydroxide, and used it to treat 25 mg / L cadmium-containing wastewater. 2+ The removal rate of Cd increased with increasing pH (4–8), resulting in... 2+ The removal rate can reach 94%. Hydroxyxamic acid can also form complexes with metal ions, exhibiting excellent selective adsorption performance. It can be used for the enrichment and recovery of valuable metals, showing broad application prospects. The adsorption of rare earth elements such as Ce, La, Pr, and Nd from seawater using polyhydroxyxamic acid showed a significantly stronger adsorption effect than that on alkali metals and alkaline earth metals, indicating that the hydroxyxamic acid has excellent selectivity.
[0004] Extensive practical experience has proven that hydroxamic acid is a class of oxide mineral collectors with high selectivity, strong collecting ability, and low toxicity and environmental friendliness, showing promising application prospects in the field of mineral flotation. Currently, it is used in the beneficiation industries of iron oxide ores, zinc oxide ores, niobium iron ore, lead-zinc ore, rare earth ores, tantalum-niobium ore, tungsten ore, cassiterite, and copper oxide ores.
[0005] Currently, there are no reports in existing technologies regarding the use of naphthylamine dihydroxyoxime compounds as mineral flotation collectors. Summary of the Invention
[0006] To address the shortcomings of existing technologies, this invention provides a hydroxamic acid flotation collector, its synthesis method, and its application.
[0007] The first objective of this invention is to provide a hydroxamic acid-based flotation collector, wherein the hydroxamic acid-based flotation collector is an amino hydroxamic acid compound having the structure of formula (1). Equation (1) Wherein, R1 is an alkylene group, an olefinene group, an aromatic group, or an alkylene ether group, and R2 is an alkane group, an olefinene group, an aromatic group, a naphthyl group, or an alkoxyether group.
[0008] Preferably, R1 is a C1-C8 alkane group or a C2-C... 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2), wherein R2 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2); Equation (2) In this context, R3 and R4 are ethylidene or propyleneide, respectively, and n is 1-3.
[0009] Preferably, R1 is methylene, ethylene, propylene, hexylene, heptylene, nonylene, allylene, or allenebutyryl.
[0010] A second objective of this invention is to provide a method for synthesizing the above-mentioned hydroxamic acid flotation collectors, the synthetic route of which is as follows: S1: Add methanol and naphthylamine to the reaction vessel, stir to disperse evenly, keep at room temperature, and then slowly add methyl haloate dropwise, and react for 3 hours; S2: Cool down to 25℃, add hydroxylamine hydrochloride under these conditions, then slowly add sodium hydroxide, and react for 0.5 h after the addition is complete; S3: Raise the temperature to 50℃ and react for 3 hours, then lower the temperature to 5℃ and add sulfuric acid at this temperature until the solution pH reaches 5. Then raise the temperature to 50℃ and react for 0.5 hours. S4: Filter the reaction solution, and remove the solvent by vacuum distillation of the filtrate to obtain the crude product of the target product. Recrystallize the crude product for further purification to obtain a purer target product.
[0011] Preferably, step S1 involves adding methanol and naphthylamine to a reaction vessel, stirring to disperse them evenly, maintaining room temperature, and then slowly adding methyl acrylate dropwise, reacting for 3 hours; the synthetic route is as follows: .
[0012] A third objective of this invention is to provide the application of the above-mentioned hydroxamic acid flotation collectors in the flotation recovery of valuable metals from non-ferrous and precious metal minerals containing rare earth elements, cassiterite, and copper oxide.
[0013] Preferably, the non-ferrous and precious metal minerals contain one or more of metals such as cerium, tin, and copper.
[0014] The beneficial effects of this invention are as follows: This invention is the first to apply naphthylaminohydroxamic acid compounds to the flotation collection of valuable metals in minerals. It is particularly suitable for the enrichment and recovery of valuable metals in oxidized minerals such as rare earth, cassiterite and copper oxide. Compared with existing commonly used collectors (such as H2O5), it can improve the recovery rate of valuable metals. Attached Figure Description
[0015] Figure 1 This is a comparison chart showing the effect of pulp pH on the flotation of fluorocarbon cerium ore using F205 and H205 in Example 1.
[0016] Figure 2 This is a comparison chart showing the effect of pulp pH on the flotation of monazite using F205 and H205 in Example 2.
[0017] Figure 3 This is a comparison chart showing the effect of pulp pH on the flotation of cassiterite using F205 and H205 in Example 3.
[0018] Figure 4 This is the infrared spectrum of F205. Detailed Implementation
[0019] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.
[0020] The technical solution of this invention is as follows: A hydroxamic acid flotation collector, wherein the hydroxamic acid flotation collector is an amino hydroxamic acid compound having the structure of formula (1). Equation (1) Wherein, R1 is an alkylene group, an olefinene group, an aromatic group, or an alkylene ether group, and R2 is an alkane group, an olefinene group, an aromatic group, a naphthyl group, or an alkoxyether group.
[0021] In some embodiments, R1 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2), wherein R2 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2); Equation (2) In this context, R3 and R4 are ethylidene or propyleneide, respectively, and n is 1-3.
[0022] In some embodiments, R1 is methylene, ethylene, propylene, hexylene, heptylene, nonylene, allylene, or allenylene.
[0023] The synthetic route for the above-mentioned hydroxamic acid flotation collectors is as follows: S1: Add methanol and naphthylamine to the reaction vessel, stir to disperse evenly, keep at room temperature, and then slowly add methyl haloate dropwise, and react for 3 hours; S2: Cool down to 25℃, add hydroxylamine hydrochloride under these conditions, then slowly add sodium hydroxide, and react for 0.5 h after the addition is complete; S3: Raise the temperature to 50℃ and react for 3 hours, then lower the temperature to 5℃ and add sulfuric acid at this temperature until the solution pH reaches 5. Then raise the temperature to 50℃ and react for 0.5 hours. S4: Filter the reaction solution, and remove the solvent by vacuum distillation of the filtrate to obtain the crude product of the target product. Recrystallize the crude product for further purification to obtain a purer target product.
[0024] In some embodiments, step S1 involves adding methanol and naphthylamine to a reaction vessel, stirring to disperse them evenly, maintaining room temperature, and then slowly adding methyl acrylate dropwise, reacting for 3 hours; the synthetic route is as follows: .
[0025] The above-mentioned hydroxamic acid flotation collectors are used in the flotation and recovery of valuable metals from non-ferrous and precious metal minerals containing rare earth elements, cassiterite, and copper oxide.
[0026] In some embodiments, the non-ferrous and precious metal minerals contain one or more of metals such as cerium, tin, and copper.
[0027] Unless otherwise specified, all parts and percentages in the examples refer to mass. The flotation and collection processes for the minerals in the examples are conventional processes, except that the phthalic acid compounds of the present invention are used to replace conventional collectors.
[0028] Example 1 When the concentrations of naphthylaminodiethylhydroxamic acid (F205) and the conventional hydroxamic acid collector 3-hydroxy-2-naphthomethylhydroxamic acid (H205) are both 6 × 10⁻⁶ -5 A flotation of fluorocarbon cerium ore with a particle size of -0.076 mm to +0.038 mm was performed for 3 minutes using a mol / L ... Figure 1 As shown, the flotation recovery rates of both were highest when the pulp pH was 8, with flotation recoveries of fluorocarbon cerium ore being 91.96% and 69.72%, respectively.
[0029] Example 2 When the concentrations of naphthylaminodiethylhydroxamic acid (F205) and the conventional hydroxamic acid collector 3-hydroxy-2-naphthomethylhydroxamic acid (H205) are both 6 × 10⁻⁶ -5 A flotation of monazite particles with a particle size of -0.076 mm to +0.038 mm was performed for 3 minutes at a concentration of mol / L and 15 mg / L of frother methyl isobutyl methanol (MIBC). The pH of the pulp was adjusted, and the results were as follows: Figure 2 As shown, the flotation recovery rates of both monazite and monazite were highest when the pulp pH was 8, with flotation recoveries of 80.25% and 55.78%, respectively.
[0030] Example 3 When the concentrations of naphthylaminodiethylhydroxamic acid (F205) and the conventional hydroxamic acid collector 3-hydroxy-2-naphthomethylhydroxamic acid (H205) are both 6 × 10⁻⁶ -5 A flotation of cassiterite with a particle size of -0.076 mm to +0.038 mm was performed for 3 minutes using a frother, methyl isobutyl methanol (MIBC), at a concentration of 15 mg / L. The pH of the pulp was adjusted, and the results were as follows: Figure 3 As shown, the flotation recovery rates of both cassiterite and cassiterite were highest when the pulp pH was 8, with the latter two being 86.25% and 57.96%, respectively.
[0031] like Figure 4As shown, the peaks corresponding to the functional groups in the molecule have all appeared, indicating that the compound synthesized in this invention is the target substance.
[0032] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or basic characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.
[0033] Where there is no conflict, the embodiments and features described above can be combined with each other. The above descriptions are merely preferred embodiments of the present invention and are not intended to limit the invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
[0034] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A hydroxamic acid-based flotation collector, characterized in that, The hydroxamic acid flotation collector is an amino hydroxamic acid compound having the structure of formula (1). Equation (1) Wherein, R1 is an alkylene group, an olefinene group, an aromatic group, or an alkylene ether group, and R2 is an alkane group, an olefinene group, an aromatic group, a naphthyl group, or an alkoxyether group.
2. The hydroxamic acid flotation collector as described in claim 1, characterized in that, R1 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2), wherein R2 is a C1-C8 alkane group, C2-C 10 olefinic group, C6-C 12 The aromatic group or the alkoxy ether group having the structure of formula (2); Equation (2) In this context, R3 and R4 are ethylidene or propyleneide, respectively, and n is 1-3.
3. The hydroxamic acid flotation collector as described in claim 2, characterized in that, R1 can be methylene, ethylene, propylene, hexylene, heptylene, nonylene, allylene, or allenebutylene.
4. A method for synthesizing a hydroxamic acid flotation collector as described in any one of claims 1-3, characterized in that, Its synthetic route is as follows: S1: Add methanol and naphthylamine to the reaction vessel, stir to disperse evenly, keep at room temperature, and then slowly add methyl haloate dropwise, and react for 3 hours; S2: Cool down to 25℃, add hydroxylamine hydrochloride under these conditions, then slowly add sodium hydroxide, and react for 0.5h after the addition is complete; S3: Raise the temperature to 50℃ and react for 3 hours, then lower the temperature to 5℃ and add sulfuric acid at this temperature until the solution pH reaches 5. Then raise the temperature to 50℃ and react for 0.5 hours. S4: Filter the reaction solution, and remove the solvent by vacuum distillation of the filtrate to obtain the crude product of the target product. Recrystallize the crude product for further purification to obtain a purer target product.
5. The method for synthesizing a hydroxamic acid flotation collector as described in claim 4, characterized in that, Step S1 involves adding methanol and naphthylamine to a reaction vessel, stirring to disperse them evenly, maintaining room temperature, and then slowly adding methyl acrylate dropwise, reacting for 3 hours; the synthetic route is as follows: 。 6. The application of a hydroxamic acid flotation collector as described in any one of claims 1-3, characterized in that, Application in the flotation and recovery of valuable metals from non-ferrous and precious metal minerals containing rare earth elements, cassiterite, and copper oxide.
7. The application of a hydroxamic acid flotation collector as described in claim 6, characterized in that, The non-ferrous and precious metal minerals contain one or more of cerium, tin, and copper.