CN113210134B - Preparation and application of acyl carboxyl azothioic ester compound - Google Patents
Preparation and application of acyl carboxyl azothioic ester compound Download PDFInfo
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- CN113210134B CN113210134B CN202110502098.0A CN202110502098A CN113210134B CN 113210134 B CN113210134 B CN 113210134B CN 202110502098 A CN202110502098 A CN 202110502098A CN 113210134 B CN113210134 B CN 113210134B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
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Abstract
The invention belongs to the technical field of mineral flotation, and particularly relates to a brand new application of an acyl carboxyl azothioic ester compound as a metal ore flotation collector. The invention discovers that the compound can generate a synergistic effect based on the molecular structure, the mutual coupling of all groups in the molecule and other effects, and can effectively improve the collecting performance of the collecting agent on metal ores.
Description
Technical Field
The invention belongs to the field of mineral flotation, and particularly relates to the technical field of a mineral flotation collector.
Technical Field
The azothioic ester compounds are an important organic compound. The compound contains S atoms with larger atomic radius and can be used as a vulcanizing agent; in addition, since the S atom in the C ═ S group has a lone pair of electrons and is liable to form a bond with a metal ion, the phosphazene compounds are widely used in the fields of rubber, petroleum, agriculture, mining, medicine, analytical chemistry and the like (lygmin, vengean, huaxiLing and the like, a synthesis and performance study of a dialkyl dithiocarbamate antioxidant and antiwear multifunctional additive [ J]Lubrication and sealing, 2009,34(9): 76-78; application of ashless thiocarbamate lubricant additive to Jun Yao soldier [ J]Synthesis of lubricating oil, 2005,20(6):41-44, Tanzao, diethyl and thiocarbamic acid rare earth complex and study of accelerated rubber vulcanization Properties [ J]Rare earth, 2000,21(3):39-41, Lotfi m.,
A.Modified activated carbon for the removal of copper,zinc,chromium and cyanide from wastewater[J].Separation and Purification Technology,2002,26(2-3):137-146.)。
the main synthetic methods of the azothionate comprise a azothionate esterification synthesis method, a xanthate ammonolysis method, a tertiary amine method and the like. The method for synthesizing the esterification of the sulfur and the nitrogen is that primary amine or secondary amine reacts with carbon disulfide under the strong alkaline condition to produce the sulfur and the nitrogen, and then reacts with a halogenating reagent to produce the sulfur and the nitrogen ester, and the method is a commonly used method (Chengxiang, N-diethyl dithiocarbamate derivative synthesis and performance [ D ] Zhongnan university, 2012). The xanthate ammonolysis method is to prepare xanthate by reacting alcohol, carbon disulfide and alkali, then the xanthate reacts with halogenated reagent to prepare xanthate, and finally the xanthate reacts with amine. The tertiary amine method is to prepare the sulfur nitrogen ester by reacting methyl or benzyl tertiary amine with carbon disulfide and alkyl halide, the price of the raw material tertiary amine used in the method is expensive, and the obtained product is difficult to separate, thereby limiting the application of the method. In addition, the collecting performance of the conventional azothionate collecting agents is to be further improved due to poor dispersing performance and less group synergistic effect.
Disclosure of Invention
The invention aims to provide a brand-new application of acyl carboxyl azothioic ester compounds in the aspect of metal ore flotation collectors.
In order to achieve the technical object of the present invention, the technical solution of the present invention is achieved as follows.
The use of acyl carboxyl azothioic ester compounds: the metal ore flotation agent is used as a collector for metal ore flotation.
The acyl carboxyl azothioic ester compound has a structure shown in formula I
In the formula I, R1Is C1～C16Alkyl of (C)2～C16Alkenyl group of (C)2～C16Alkynyl of (2), C5～C16Cycloalkyl or C6～C16Aryl of (a);
the alkyl, the alkenyl, the alkynyl, the cyclic group and the aryl are allowed to have substituents; the substituent is C1～C6Alkyl of (C)1～C6Alkoxy group of (C)1～C6At least one of alkylthio, hydroxyl and phenyl;
R2is C1～C8An alkylene group of (a).
The inventor innovatively finds that the collecting agent has a sulfur-nitrogen ester group and an acyl groupThe group and the carboxyl multifunctional group cooperate with each other in the molecule, so that the collecting performance of the collector can be improved from the molecular layer, and the collector can be endowed with good dispersing performance unexpectedly, thereby enhancing the flotation effect on metal minerals. Furthermore, it has been found that by applying R1、R2The optimization can further improve the synergistic performance of functional groups in molecules, and further improve the dispersing performance and the collecting performance of the collecting agent in ore pulp. In formula I, the alkyl is, for example, a straight chain or branched chain alkyl; the cycloalkyl group may be a saturated or partially unsaturated cycloalkyl group; the aryl group is, for example, benzene or a fused ring group formed by the union of two or more benzene rings, or a heterocyclic aryl group.
The alkyl, the alkylene, the alkynyl, the saturated cycloalkyl, the partially unsaturated cycloalkyl and the aryl are allowed to contain substituent groups which are respectively substituted alkyl, substituted alkylene, substituted alkynyl, substituted cyclic and substituted aryl. Preferably, said substituent is for example C1～C6Alkyl of (C)1～C6Alkoxy group of (C)1～C6At least one of alkylthio, hydroxyl and phenyl.
Preferably, in formula I, R is1Is selected from C1～C16Saturated alkyl or alkoxyalkyl of C2～C16Alkyl alkenyl of, C2～C16Alkyl alkynyl of (2), C5～C16A cycloalkane group of6～C16Aromatic hydrocarbon groups, aromatic hydrocarbon alkyl groups, etc.
Further preferably, R1Selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, undecyl, pentadecyl, ethoxyethyl, tert-butoxyethyl, phenyl, benzyl, phenethyl, styryl, m-methylphenyl, p-ethylphenyl, p-methoxyphenyl, cyclopropyl, cyclopentyl, cyclohexyl, propenyl, or propynyl.
Even more preferably, R1Selected from n-heptyl, n-octyl, isooctyl, n-nonyl, undecyl, phenyl or benzyl. The inventors have found that at selected R1In the next step, intramolecular synergy of the collector structure can be further improved, and the collecting performance and flotation selectivity can be further improved.
R2Is- (CH)2)mPreferably, m is 1 to 8.
Preferably, R2Is 1, 2-methylene, 1, 3-propylene, 1, 2-isopropylene, 1, 4-butylene, 1, 3-isobutylene, 1, 2-tert-butylene, 1, 5-pentylene, 1, 4-isopentylene or 1, 6-hexylene.
More preferably, m is 1 to 3. The inventors have found that at selected R2And the collecting agent has better dispersibility in ore pulp and stronger collecting effect.
The acyl carboxyl azothioic ester compound can be prepared by the following method:
acyl halide with a structure shown in a formula II, thiocyanate with a structure shown in a formula III and mercaptoalkyl carboxylic acid with a structure shown in a formula IV are used as raw materials, an organic compound is used as a solvent, and the acyl carboxyl nitrogen sulfate with the structure shown in the formula I is prepared by a one-pot method.
In the formula II, X is Cl, Br or I;
MSCN
formula III
In the formula III, M is NH4 +、Na+Or K+；
In the formula IV, R2Is C1～C12An alkylene group of (a).
The acyl carboxyl thionin ester with the structure of formula I is prepared by reacting acyl halide with the structure of formula II, thiocyanate with the structure of formula III and mercaptoalkylcarboxylic acid with the structure of formula IV as raw materials and an organic compound as a solvent in a one-pot method. The specific synthetic route is shown as formula (1):
in the formula (1), X is Cl, Br or I; m is NH4 +、Na+Or K+。
The preparation method of the acyl carboxyl azothioic ester compound comprises the following steps:
sequentially adding a catalyst, a solvent and thiocyanate shown in a formula III into a reaction bottle, then dropwise adding acyl halide shown in a formula II below 10 ℃, and reacting for 0.5-8 h at 0-80 ℃ after dropwise adding; after the reaction is finished, filtering to remove salt, and then carrying out rotary evaporation to recover the solvent; and adding the mercaptoalkyl carboxylic acid shown in the formula IV into a reaction bottle, and reacting for 0.5-10 h at the temperature of 5-80 ℃ after the addition is finished. Cooling, adding petroleum ether, and separating out solid, namely the acyl carboxyl azothioic ester compound.
Preferably, the method comprises the following steps: the ratio of the amounts of the acyl halide, thiocyanate and mercaptoalkylcarboxylic acid is 1: 1.0-1.5;
preferably, the method comprises the following steps: the solvent is dichloromethane, acetonitrile, toluene, acetone, dimethylformamide and dimethyl sulfoxide;
preferably, the method comprises the following steps: the amount of the solvent is 5-100 ml of the solvent per 0.1mol of acyl halide.
Preferably, the method comprises the following steps: a catalyst is added in the reaction process, and the catalyst is at least one of aryl amines and polyethylene glycols.
Preferably, the arylamine catalyst is at least one of N, N-dimethylaniline, N-dimethyl-p-methylamine and N, N-diethylaniline;
preferably, the polyethylene glycol catalyst is at least one of PEG-200, PEG-400, PEG-600 or PEG-800.
The catalyst is used in catalytic amounts.
The invention also provides the application of the acyl carboxyl azothioic ester compound (the compound shown in the formula I) or the acyl carboxyl azothioic ester compound (the compound shown in the formula I) prepared by the preparation method for the first time, and the acyl carboxyl azothioic ester compound is used as a flotation collector for the flotation of metal minerals.
Preferably, the metal mineral is a non-ferrous metal mineral. The collector of the invention can be suitable for the high-efficiency flotation of sulphide ores and/or oxide ores.
More preferably, the metal ore is at least one of non-ferrous metal ores such as chalcopyrite, pyrite, bornite, galena, sphalerite, malachite, cassiterite, scheelite, wolframite and fluorite.
In the application, in the process of grinding and/or flotation of metal ores, a flotation reagent containing a collecting agent with a structure shown in a formula I is added, and concentrate is floated and separated by a froth flotation method after size mixing.
The basic process of using the acyl carboxyl azothioic ester compound as the flotation collector comprises the following steps: (a) finely grinding ores and then performing flotation; (b) adding a flotation reagent for size mixing in the ore grinding and/or flotation processes, wherein the added reagent at least contains one acyl carboxyl azothioic ester compound; (c) the useful metal minerals are floated by a froth flotation method.
The flotation condition of the non-ferrous metal minerals is to maintain the pH of the ore pulp to be 2-12; preferably 5 to 10. The inventors have found that at the preferred pH, there is better collection performance, for example, higher collection recovery.
The dosage of the acyl carboxyl azothioic ester compound in the ore pulp is 5-1000 g/t mineral. Preferably, the ore with the pulp granularity of-200 meshes accounts for 60-100% of the whole ore mass.
The invention also provides a flotation reagent for metal minerals, which comprises the collector shown in the formula I and other auxiliary agents allowed to be added in the flotation field, such as a foaming agent. The foaming agent may be a material known in the industry to have foaming properties, such as MIBC.
The invention has the advantages of
The invention discovers for the first time that the acyl carboxyl azothioic ester compound has good collecting performance and metal separation selectivity when being used as the flotation collecting agent of metal minerals.
According to the collector disclosed by the invention, due to the conjugated effect between C ═ O and C ═ S in a molecule, two groups can act with the same metal ion and form a six-membered ring structure, the chelating capacity of the collector molecule to the metal on the surface of the mineral is enhanced, and the collector has good collecting performance to sulfide ore and oxidized ore. In addition, the terminal R is further matched on the basis of intramolecular synergy of-CO-N-CS-S1And the combined control of carboxyl groups is beneficial to further improving the chelating, dispersing and foaming properties of the collector, thereby improving the collecting capability of the collector.
In addition, the invention also provides a one-pot synthesis means of the collecting agent, and the synthesis method is simple to operate and has good reaction effect.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of S-carboxyethyl-N-benzoyl dithiocarbamate;
FIG. 2 is a nuclear magnetic carbon spectrum of S-carboxyethyl-N-benzoyldithiocarbamate;
FIG. 3 is a nuclear magnetic hydrogen spectrum of S-carboxyethyl-N-octanoyl dithiocarbamate;
FIG. 4 is a nuclear magnetic carbon spectrum of S-carboxyethyl-N-octanoyldithiocarbamate;
Detailed Description
The invention is further illustrated by, but is not limited to, the following examples. All parts and percentages in the examples are by mass unless otherwise specified.
Example 1: preparation of S-carboxyethyl-N-benzoyl dithiocarbamate
Adding 1.15 parts of PEG-400 with the purity of 99%, 8.27 parts of NaSCN with the purity of 98% and 80 parts of dichloromethane with the purity of 99% into a 250mL three-neck flask, stirring for 10 minutes at the temperature of 10 ℃, then adding 14.20 parts of benzoyl chloride with the purity of 99%, heating to 25 ℃ after finishing dripping, reacting for 3.5 hours, filtering to remove salt after the reaction is finished, and performing rotary evaporation to recover the dichloromethane. Then 9.40 parts of 2-mercaptoacetic acid with a purity of 98% was added to the reaction vessel, and the temperature was raised to 35 ℃ for 4 hours. After the reaction is finished, petroleum ether is added to separate out yellowAnd (3) filtering the solid to obtain a crude product of the S-carboxyethyl-N-benzoyl dithiocarbamate, wherein the purity of the product is 84.56%, and the yield based on 2-mercaptoacetic acid is 88.13%. The crude product of the S-carboxyethyl-N-benzoyl dithiocarbamate is subjected to structural characterization after recrystallization and purification by ethanol/water,1h NMR and13the C NMR charts are shown in FIG. 1 and FIG. 2, respectively. It is composed of1H NMR and13the results of C NMR analysis are shown in Table 1.
Example 2: preparation of S-carboxyethyl-N-octanoyl dithiocarbamate
1.15 parts of PEG-400 with the purity of 99%, 8.27 parts of NaSCN with the purity of 98% and 80 parts of dichloromethane with the purity of 99% are added into a 250mL three-neck flask, stirred for 10 minutes within 10 ℃, then added with 16.43 parts of octanoyl chloride with the purity of 99%, heated to 40 ℃ and reacted for 3.5 hours. After the reaction, the solution is filtered to remove salt, methylene chloride is recovered by rotary evaporation, 9.40 parts of 2-sodium thioglycolate with the purity of 98 percent is added into a reaction vessel, and the temperature is raised to 40 ℃ for reaction for 4 hours. After the reaction is finished, petroleum ether is added to separate out yellow solid, and the crude product of the S-carboxyethyl-N-octanoyl dithiocarbamic acid ester is obtained after filtration, wherein the purity of the product is 83.45 percent, and the yield based on the 2-sodium thioglycolate is 86.27 percent. The crude product is purified by ethanol/water recrystallization and then subjected to structural analysis, which1H NMR and13the C NMR charts are shown in FIG. 3 and FIG. 4, respectively. It is composed of1H NMR and13the results of C NMR analysis are shown in Table 1.
TABLE 1 preparation of the desired products1H NMR and13c NMR analysis
Example 3: flotation of chalcopyrite by S-carboxyethyl-N-benzoyl dithiocarbamate
At a concentration of S-carboxyethyl-N-benzoyldithiocarbamate of2×10-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the chalcopyrite with the granularity of-0.076 mm to +0.038mm is floated for 3 minutes, and the flotation recovery rate of the chalcopyrite is 96.23 percent.
Comparative example 1: flotation of chalcopyrite by S-carboxyethyl-N-benzyl dithiocarbamate
At a concentration of 2X 10S-carboxyethyl-N-benzyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the chalcopyrite with the granularity of-0.076 mm to +0.038mm is floated for 3 minutes, and the flotation recovery rate of the chalcopyrite is 90.88 percent.
Comparative example 2: flotation of chalcopyrite by S-ethyl-N-benzyl dithiocarbamate
At a concentration of 2X 10S-ethyl-N-benzyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, chalcopyrite with the granularity of-0.076 mm to +0.038mm is floated for 3 minutes, and the flotation recovery rate of the chalcopyrite is 91.35%.
Example 4: flotation of malachite with S-carboxyethyl-N-benzoyldithiocarbamate
At a concentration of 2X 10S-carboxyethyl-N-benzoyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the floatation of the malachite with the granularity of-0.076 mm to +0.038mm is carried out for 3 minutes, and the floatation recovery rate of the malachite is 92.44 percent.
Comparative example 3: flotation of malachite with benzoic acid
At a benzoic acid concentration of 2X 10-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10- 4mol/L，N2The flow rate is 200mL/min, the floatation of the malachite with the granularity of-0.076 mm to +0.038mm is carried out for 3 minutes, and the floatation recovery rate of the malachite is 45.11 percent.
Example 5: flotation of pyrite with S-carboxyethyl-N-benzoyl dithiocarbamate
At a concentration of 2X 10S-carboxyethyl-N-benzoyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the pyrite with the granularity of-0.076 mm to +0.038mm is floated for 3 minutes, and the flotation recovery rate of the pyrite is 38.76 percent.
Example 6: flotation of artificial mixed ore of chalcopyrite and pyrite by S-carboxyethyl-N-benzoyl dithiocarbamate
Comparing the flotation selectivity of S-carboxyethyl-N-benzoyl dithiocarbamate to chalcopyrite and pyrite by common sulfide collecting agents, the concentration of the collecting agents is 2 multiplied by 10-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate was 200mL/min, and the artificial mixed ore of chalcopyrite and pyrite (chalcopyrite and pyrite both having a mass of 1.0g) having a particle size of-0.076 mm to +0.038mm was floated for 3 minutes, and the flotation results are shown in Table 2.
TABLE 2 results of artificial bulk flotation of chalcopyrite and pyrite
Example 7: flotation of S-carboxyethyl-N-benzoyl dithiocarbamate against galena
At a concentration of 1X 10S-carboxyethyl-N-benzoyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the galena with the granularity of-0.076 mm to +0.038mm is floated for 3 minutes, and the flotation recovery rate of the galena is 96.08 percent.
Example 8: flotation of malachite with S-carboxyethyl-N-octanoyl dithiocarbamate
At a concentration of 5X 10 of S-carboxyethyl-N-octanoyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, and the particle size is-0.076 mm- +0.038mm of malachite ore is floated for 3 minutes, and the flotation recovery rate of the malachite is 95.62%.
Example 9: flotation of S-carboxyethyl-N-octanoyl dithiocarbamate on cassiterite
At a concentration of 5X 10 of S-carboxyethyl-N-octanoyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the cassiterite with the granularity of-0.076 mm- +0.038mm is floated for 3 minutes, and the flotation recovery rate of the cassiterite is 94.21 percent.
Example 10: flotation of scheelite with S-carboxyethyl-N-octanoyl dithiocarbamate
At a concentration of 5X 10 of S-carboxyethyl-N-octanoyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the scheelite with the granularity of-0.076 mm to +0.038mm is floated for 3 minutes, and the flotation recovery rate of the scheelite is 93.23%.
Example 11: flotation of fluorite with S-carboxyethyl-N-octanoyl dithiocarbamate
At a concentration of 5X 10 of S-carboxyethyl-N-octanoyldithiocarbamate-5mol/L, pH of the pulp 8.0, and concentration of frother (MIBC) 1.5X 10-4mol/L，N2The flow rate is 200mL/min, the fluorite with the granularity of-0.076 mm to +0.038mm is floated for 3 minutes, and the flotation recovery rate of the fluorite is 94.15 percent.
Based on the above experimental results, it is revealed that the synergistic effect of C-O, C-S and COOH can significantly improve the flotation capability of the collector on metal minerals. In addition, by further fitting R of the end portion1And the combined control of carboxyl groups is beneficial to further improving the chelating, dispersing and foaming properties of the collector, thereby improving the collecting capability of the collector.
The acyl carboxyl azothioic ester collecting agent is obtained by using acyl halide, thiocyanate and mercapto alkyl carboxylic acid as raw materials and organic matter as a solvent through a one-pot reaction. The invention also creatively applies the acyl carboxyl sulfur nitrogen ester collecting agent to the flotation of the nonferrous metal ores, and the flotation result shows that the acyl carboxyl sulfur nitrogen ester collecting agent has stronger collecting capability on sulfide ores and oxidation.
Claims (20)
1. The application of the acyl carboxyl azothioic ester compound as a metal ore collecting agent is characterized in that the acyl carboxyl azothioic ester compound is used as the collecting agent for the flotation of metal ores;
the acyl carboxyl azothioic ester compound has a structure shown in a formula I:
formula I
In the formula I, R1Is C1~C16Alkyl of (C)2~C16Alkenyl group of (C)2~C16Alkynyl of (2), C5~C16Cyclic group of (A) or (C)6~C16Aryl of (a);
the alkyl, the alkenyl, the alkynyl, the cyclic group and the aryl are allowed to have substituents; the substituent is C1~C6Alkyl of (C)1~C6Alkoxy group of (C)1~C6At least one of alkylthio, hydroxyl and phenyl;
R2is C1~C8An alkylene group of (a).
2. Use according to claim 1, characterized in that R1Selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, undecyl, pentadecyl, ethoxyethyl, tert-butoxyethyl, phenyl, benzyl, phenethyl, styryl, m-methylphenyl, p-ethylphenyl, p-methoxyphenyl, cyclopropyl, cyclopentyl, cyclohexyl, propenyl, or propynyl.
3. Use according to claim 1, characterized in that R1Is n-heptyl, n-octyl, isooctyl, n-nonyl, undecyl, phenyl or benzyl.
4. Use according to claim 1, characterized in that R2Is- (CH)2)m-, m is 1 to 8.
5. Use according to claim 4, wherein R is2Is 1, 2-methylene, 1, 3-propylene, 1, 2-isopropylene, 1, 4-butylene, 1, 3-isobutylene, 1, 2-tert-butylene, 1, 5-pentylene, 1, 4-isopentylene or 1, 6-hexylene.
6. The use according to any one of claims 1 to 5, wherein the collector with the structure of formula I is prepared by reacting an acyl halide with the structure of formula II, a thiocyanate with the structure of formula III, and a mercaptoalkyl carboxylic acid with the structure of formula IV:
formula II
In the formula II, X is Cl, Br or I;
MSCN
formula III
In the formula III, M is NH4 ＋、Na+Or K+；
Formula IV.
7. The use according to claim 6, wherein the ratio of the amounts of the substance of acyl halide, thiocyanate and mercaptoalkylcarboxylic acid is 1:1.0 to 1.5.
8. The use according to claim 6, wherein the solvent of the reaction process is at least one of dichloromethane, acetonitrile, toluene, acetone, dimethylformamide, and dimethylsulfoxide.
9. The use according to claim 8, characterized in that the amount of the solvent is 5 to 100ml of the solvent per 0.1mol of the acid halide.
10. The use according to claim 6, wherein a catalyst is added in the reaction process, and the catalyst is at least one of an arylamine catalyst and a polyethylene glycol catalyst.
11. Use according to claim 10, characterized in that the arylamine catalyst is at least one of N, N-dimethylaniline, N-dimethyl-p-methylamine, N-diethylaniline.
12. The use according to claim 10, wherein the polyethylene glycol catalyst is at least one of PEG-200, PEG-400, PEG-600, or PEG-800.
13. The use according to claim 10, wherein the catalyst, the solvent and the thiocyanate of the formula III are added into a reaction bottle in sequence, then the acyl halide of the formula II is dropwise added at the temperature of below 10 ℃, and after the dropwise addition is finished, the reaction is carried out for 0.5 to 8 hours at the temperature of 0 to 80 ℃; after the reaction is finished, filtering to remove salt, and then carrying out rotary evaporation to recover the solvent; adding the mercaptoalkylcarboxylic acid shown in the formula IV into a reaction bottle, and reacting at the temperature of 5-80 ℃ for 0.5-10 h; cooling, adding petroleum ether, and separating out solid, namely the acyl carboxyl azothioic ester compound.
14. Use according to any one of claims 1 to 5, characterized in that the pH of the pulp is maintained between 2 and 12 during flotation.
15. Use according to claim 14, characterized in that the pH of the pulp is maintained between 5 and 10 during flotation.
16. The use according to any one of claims 1 to 5, wherein the amount of the acyl carboxyl azothioic ester compound in the ore pulp is 5 to 1000g/t mineral.
17. The use according to any one of claims 1 to 5, characterized in that ore pulp in the flotation process with a particle size of-200 meshes accounts for 60 to 100 percent of the whole ore mass.
18. Use according to claim 1, wherein the metal mineral is at least one of sulphide ore or oxide ore.
19. The use according to claim 18, wherein the metal mineral is at least one of chalcopyrite, pyrite, bornite, galena, sphalerite, molybdenite, malachite, cassiterite, scheelite, wolframite, fluorite, bauxite.
20. A metal ore flotation reagent comprising a collector of formula I according to any one of claims 1 to 19 and a frothing agent.
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