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CN-121972299-A - Diphenyl bridged bishydroxamic acid flotation collector and preparation method and application thereof

CN121972299ACN 121972299 ACN121972299 ACN 121972299ACN-121972299-A

Abstract

The invention belongs to the technical field of mineral processing and beneficiation reagents, and particularly relates to a diphenyl bridged bis-hydroxamic acid flotation collector, a preparation method and application thereof. The chemical general formula of the diphenyl bridged bishydroxamic acid flotation collector is HO-NHC (=O) -Ar-O-R-O-Ar-C (=O) -NHOH, wherein Ar is an aromatic ring group with carboxyl or carboxylate groups at the ortho position, and R is alkylene with 1-8 carbon atoms. The collector with the double benzene ring and double hydroxamic acid structure provided by the invention is expected to have stronger selectivity, more stable chelating capacity and higher hydrophobicity, so that excellent collecting effect and sorting efficiency are shown in the flotation process, and the defects of insufficient selectivity, poor hydrophobicity and the like of the existing hydroxamic acid medicament are effectively overcome.

Inventors

  • GAO PENG
  • HE JIAHAO
  • YUAN SHUAI
  • HAN YUEXIN
  • LI YANJUN

Assignees

  • 东北大学

Dates

Publication Date
20260505
Application Date
20260327

Claims (10)

  1. 1. A diphenyl bridged bishydroxamic acid flotation collector is characterized by having a chemical general formula of HO-NHC (=O) -Ar-O-R-O-Ar-C (=O) -NHOH; wherein Ar is an aromatic ring group with carboxyl or carboxylate group at the ortho position, and R is alkylene with 1-8 carbon atoms.
  2. 2. The diphenyl bridged bis hydroxamic acid flotation collector of claim 1, wherein R is a propylene of 3 carbon atoms.
  3. 3. The diphenyl bridged bishydroxamic acid flotation collector of claim 1, having the chemical formula HO-NHC (=o) -C 6 H 4 –O–(CH 2 ) 3 –O–C 6 H 4 -C (=o) -NHOH.
  4. 4. A method for preparing the diphenyl bridged bis-hydroxamic acid flotation collector according to any one of claims 1 to 3, comprising the steps of: (1) Reacting a hydroxy aromatic carboxylate with a dihaloalkane under alkaline conditions to obtain a diester diether intermediate; (2) And reacting the diester diether intermediate with hydroxylamine or a salt thereof to obtain the diphenyl bridged bis-hydroxamic acid flotation collector.
  5. 5. The preparation method of claim 4, wherein in the step (1), the molar ratio of the hydroxy aromatic carboxylic ester to the dihaloalkane is 1:0.25-2, the reaction temperature is 20-130 ℃, the reaction time is 0.5-12 h, the acid binding agent used in the reaction process is sodium ethoxide or potassium carbonate, and the solvent is any one of methanol, ethanol, acetone or DMF.
  6. 6. The method according to claim 4, wherein the molar ratio of the diester diether intermediate to hydroxylamine or a salt thereof in the step (2) is 1:0.25-2, the reaction temperature is 20-80 ℃, and the reaction time is 0.5-12 hours.
  7. 7. The method according to claim 4, wherein, The hydroxy aromatic carboxylic acid ester comprises any one of methyl o-hydroxybenzoate, methyl 3-hydroxybenzoate, methyl 4-hydroxybenzoate, methyl polyhydroxy benzoate, methyl amino-hydroxybenzoate and methyl halogen-hydroxybenzoate; The dihaloalkane comprises any one of 1, 4-dibromopropane, dibromomethane, dibromoethane, dibromobutane, dichloroethane and dichloromethane; the hydroxylamine or a salt thereof includes any one of hydroxylamine hydrochloride, hydroxylamine sulfate, hydroxylamine phosphate or a salt thereof.
  8. 8. The method according to claim 7, wherein the hydroxy aromatic carboxylic acid ester is methyl o-hydroxybenzoate, the dihaloalkane is 1, 4-dibromopropane, and the hydroxylamine or a salt thereof is hydroxylamine hydrochloride.
  9. 9. The use of a diphenyl bridged bis hydroxamic acid flotation collector according to any one of claims 1 to 3, for the flotation of metal oxide ores, wherein the metal oxide ores are metal oxide ores comprising at least one of tungsten, tin, titanium, iron, copper, lead, rare earth.
  10. 10. The use according to claim 9, characterized in that the addition of the diphenyl bridged bishydroxamic acid flotation collector is 1-1000 g/t relative to the mass of the raw ore, and the flotation pH interval is 6-10.

Description

Diphenyl bridged bishydroxamic acid flotation collector and preparation method and application thereof Technical Field The invention belongs to the technical field of mineral processing and beneficiation reagents, and particularly relates to a diphenyl bridged bis-hydroxamic acid flotation collector, a preparation method and application thereof. Background The hydroxamic acid collector can form stable chelate with transition metal ions and rare earth metal ions, and is widely applied to the field of mineral flotation. The hydroxyl oxygen, oximido oxygen and nitrogen atoms in the hydroxamic acid molecule all have rich lone pair electrons, so that the hydroxamic acid can form stable chelate complexes with various metal ions such as Fe 3+、Fe2+、RE3+、Pb2+、Co2+、Ti4+, sn 4+ and the like. This characteristic makes hydroxamic acid compounds excellent in the flotation of rare earth, ilmenite, tungsten, tin, copper oxide and iron ore metal ores. The most commonly used hydroxamic acid agents in the industry today are of the monohydroxamic acid structure, i.e. contain only one hydroxamic acid group per molecule. Depending on the hydrophobic groups of the molecule, such collectors can be classified into aromatic and aliphatic hydroxamic acids. The former typically represents benzoic hydroxamic acid and salicylic hydroxamic acid, which have aromatic rings as hydrophobic groups and have been widely used for flotation separation of oxidized minerals such as tungsten ores and rare earth ores, while the latter represents alkyl hydroxamic acids (e.g., octyl hydroxamic acid) which have aliphatic hydrocarbon chains as hydrophobic ends and have been studied for use in the flotation of minerals such as tungsten tin. However, in general, the conventional hydroxamic acid collectors have the problems of single structure and improved performance. In response to the problem of insufficient hydrophobicity of hydroxamic acid collectors, researchers have made many improvements. For example, application of O-allyl salicylhydroxamic acid compound in metal mineral flotation, 3-allyl salicylhydroxamic acid compound in Chinese patent No. CN115228618A, preparation thereof and application in metal mineral flotation all disclose that longer hydrophobic chains or hydrophobic groups (such as alkoxy, allyl and the like) are introduced into aromatic hydroxamic acid molecules, so that novel collectors of alkoxy benzoic hydroxamic acid, allyl salicylhydroxamic acid and the like are developed, the hydrophobicity of molecules is obviously enhanced, and the collection capacity of the novel collectors on metal oxide ores is improved. In addition, the prior art strengthens the collection performance by increasing the number or variety of functional groups in the hydroxamic acid molecule, for example, chinese patent No. CN104888969A, CN106955790A, CN118255701a discloses a series of modified hydroxamic acid structures containing double functional groups, and by introducing a plurality of hydroxamic acid groups or other chelating/hydrophobic functional groups in the same molecule, the multi-site adsorption of the medicament on the mineral surface is enhanced, and the collection effect is further improved. Disclosure of Invention The invention designs a novel flotation collector of double benzene ring and double hydroxamic acids. On the molecular structure, a symmetrical 'double benzene ring' rigid framework is introduced, and the middle is connected through a proper bridge bond, so that two ends respectively carry a hydroxamic acid chelating group. Through the molecular design of the 'double benzene ring-bridging-double hydroximoyl', the selectivity of the collector to the target oxidized mineral can be obviously improved, and stronger and more stable chelating coordination capacity is provided. Meanwhile, the increased hydrophobic groups of the aromatic rings in the molecules can improve the degree of hydrophobicity imparted to the surface of the mineral by the medicament, promote the combination of ore particles and bubbles and improve the flotation efficiency. The collector with the double benzene ring and double hydroxamic acid structure provided by the invention is expected to have stronger selectivity, more stable chelating capacity and higher hydrophobicity, so that excellent collecting effect and sorting efficiency are shown in the flotation process, and the defects of insufficient selectivity, poor hydrophobicity and the like of the existing hydroxamic acid medicament are effectively overcome. The first object of the invention is to provide a novel double hydroxamic acid type flotation collector, which adopts a molecular framework with two rigid aromatic groups, two hydroxamic acid head groups and a flexible ether bridge structure, so that the reagent has stronger coordination capacity and interface activity, and the flotation separation effect of oxide ores such as rare earth minerals is improved. In order to achieve the above object, the present inv